Photochromic compound, curable composition, optical article, lens, and glasses

Abstract

The purpose of the present disclosure is to provide: a photochromic compound having excellent repeated durability and solubility in a matrix material; a curable composition containing the photochromic compound; an optical article; a lens; according to one embodiment, a photochromic compound having a skeleton represented by formula (1) is provided. In formula (1), M is C, Si, or Ge. R1 is a hydrogen atom or a substituent group. And when R1 is a substituent, R1 is not a halogen atom or a trifluoromethyl group. And R2 is a hydrogen atom or a substituent group. And when R2 is a substituent, R2 is not a halogen atom. And R3 and R4 are respectively and independently straight-chain or branched-chain alkyl. And R3 and R4 have different structures from each other.

Description

Technical Field

[0001] This invention relates to photochromic compounds, curable compositions, optical articles, lenses, and eyeglasses. Background Technology

[0002] Photochromic compounds are compounds that can reversibly acquire two isomers with different absorption spectra when exposed to ultraviolet light, such as sunlight or mercury lamp light. Generally, by irradiating a colorless, achromatic compound with ultraviolet light, its color changes rapidly, isomerizing into a colored, chromogenic state (a colorimetric reaction). Photochromic compounds have been researched and developed as materials, for example, for photochromic lenses.

[0003] In the application of such photochromic lenses, photochromic compounds sometimes require the following properties.

[0004] (I) The chromaticity (hereinafter referred to as initial chromaticity) in the visible light region before ultraviolet irradiation is small.

[0005] (II) High speed from the start of ultraviolet irradiation to the saturation of color development concentration (hereinafter referred to as color development concentration) (hereinafter also referred to as high color development sensitivity).

[0006] (III) The rate at which the irradiation of ultraviolet light stops and the color returns to its original state (hereinafter referred to as the fading rate) is high.

[0007] (IV) The reversible effects described above have high durability.

[0008] As photochromic compounds that satisfy these properties, a large number of chromene compounds have been studied. For example, chromene compounds represented by the following formula (A) (Patent Document 1), chromene compounds represented by the following formula (B) (Patent Document 2), and chromene compounds represented by the following formula (C) (Patent Document 3) are known.

[0009] Photochromic lenses containing these photochromic compounds can be manufactured by various methods. For example, there is a method of impregnating the lens surface with a photochromic compound. Another method is to use a cured product of a photochromic curable composition as a photochromic lens. Furthermore, there is a method of laminating a cured product of a photochromic curable composition, i.e., a photochromic layer, onto an optical substrate to obtain a photochromic laminate. The method of laminating a photochromic layer onto an optical substrate is applicable to various optical substrates and is therefore advantageous. The photochromic curable composition, for example, includes a matrix material such as (meth)acrylate or isocyanate and a photochromic compound (see Patent Documents 4, 5, and 6).

[0010]

[0011]

[0012]

[0013] Existing technical documents

[0014] Patent documents

[0015] Patent Document 1: International Publication No. 1996 / 014596

[0016] Patent Document 2: International Publication No. 2004 / 085568

[0017] Patent Document 3: International Publication No. 2011 / 053615

[0018] Patent Document 4: International Publication No. 2011 / 125956

[0019] Patent Document 5: International Publication No. 2020 / 094772

[0020] Patent Document 6: Japanese Patent Application Publication No. 2021-59681

[0021] Patent Document 7: Japanese Patent Application Publication No. 2019-182866

[0022] Patent Document 8: International Publication No. 2013 / 042800

[0023] Patent Document 9: International Publication No. 2015 / 035325

[0024] Patent Document 10: International Publication No. 2018 / 235771

[0025] Patent Document 11: Japanese Patent Application Publication No. 2018-62496

[0026] Patent Document 12: International Publication No. 2021 / 075456

[0027] Patent Document 13: U.S. Patent Application Publication No. 2006 / 0022176

[0028] Patent Document 14: International Publication No. 2016 / 143910 Summary of the Invention

[0029] The problem the invention aims to solve

[0030] The object of the present invention is to provide a photochromic compound with excellent repeatability and durability and excellent solubility in a matrix material, a curable composition containing the photochromic compound, optical articles, lenses and eyeglasses.

[0031] Solution for solving the problem

[0032] According to this disclosure, a photochromic compound having a skeleton as shown in the following formula (3) is provided.

[0033]

[0034] In equation (3), M is C, Si, or Ge. 1 It can be a hydrogen atom or a substituent. In R 1 In the case of a substituent, it is not a halogen atom or a trifluoromethyl group. R 2 It can be a hydrogen atom or a substituent. In R 2 In the case of a substituent, it is not a halogen atom. R 3 and R 4 Each is an alkyl group, either straight-chain or branched. R 3 and R 4 They have different structures from each other. R 5 and R 6 Each can be an independent hydrogen atom or a substituent. R 7 and R 8 Each is an independent substituent. b and c are each an independent integer of 0, or 1 or more but less than 3.

[0035] According to this disclosure, a curable composition is provided. The curable composition comprises the photochromic compound of the embodiments; and at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)carbamate (urea) polymer.

[0036] According to this disclosure, an optical article is provided. The optical article comprises a cured product of a curable composition.

[0037] According to this disclosure, a lens is provided. The lens comprises a photochromic compound according to an embodiment.

[0038] According to this disclosure, eyeglasses are provided. The eyeglasses include lenses according to embodiments.

[0039] The effects of the invention

[0040] According to the present invention, photochromic compounds with excellent repeatability and solubility, curable compositions comprising the photochromic compounds, optical articles, lenses and eyeglasses can be provided. Detailed Implementation

[0041] [Photochromic compounds]

[0042] In photochromic laminates, the photochromic layer is required to be a relatively thin film to utilize the properties of the optical substrate. However, thinning the photochromic layer can sometimes reduce its repeated durability. Furthermore, to achieve sufficient photochromic properties in a thin film, the photochromic compound needs to be dispersed in the photochromic layer at a high concentration. Therefore, in addition to the characteristics mentioned above, the photochromic compound should also have high solubility in the matrix material and high dispersibility within the matrix. On the other hand, photochromic compounds with excessively high solubility in the matrix material are difficult to crystallize, making it difficult to remove trace impurities through purification. Due to the influence of these impurities, the photochromic compound deteriorates, making it difficult for the isomerization reaction of the photochromic compound to occur, which may reduce repeated durability.

[0043] According to an embodiment, a photochromic compound having a skeleton as shown in the following formula (3) is provided.

[0044]

[0045] In equation (3), M is C, Si, or Ge. 1 It can be a hydrogen atom or a substituent. In R 1 In the case of substituents, it is not a halogen atom, and is a trifluoromethyl group. R 2 It can be a hydrogen atom or a substituent. In R 2 In the case of a substituent, it is not a halogen atom. R 3 and R 4 Each is an alkyl group, either straight-chain or branched. R 3 and R 4 They have different structures from each other. R 5 and R 6 Each can be an independent hydrogen atom or a substituent. R 7 and R 8 Each is an independent substituent. b and c are each an independent integer of 0, or 1 or more but less than 3.

[0046] This photochromic compound exhibits excellent durability and solubility. The reasons for this are not yet clear, but the inventors believe the following.

[0047] The aforementioned R is bonded to atom M at position 13 of the photochromic compound in the embodiment. 3 and R 4 Its characteristic is that the R 3 and R 4The compounds are alkyl groups, but with different structures. The solubility of the photochromic compound in the matrix material is considered to be influenced by both its affinity for the matrix material and the flexibility of its crystal structure. It is believed that because the photochromic compound of the embodiment has an alkyl group with a different structure substituted at the 13-position M atom, the symmetry of the molecule is moderately reduced, and the intermolecular interactions of the photochromic compound are weakened. As a result, the flexibility of the crystal structure of the photochromic compound is considered to be improved. Furthermore, the crystallinity of the photochromic compound is not completely lost; therefore, high-purity photochromic compounds can be obtained through methods such as recrystallization. Therefore, it is believed that the reduction in repeated durability caused by the degradation of the photochromic compound due to impurities can also be suppressed. Therefore, the photochromic compound of the embodiment achieves high solubility in various matrix materials and exhibits high durability.

[0048] Furthermore, the inventors conducted in-depth research and discovered that by introducing a substituent R onto the atom M at position 13 without passing through an oxygen atom (O), the problem can be solved. 3 and R 4 The durability of the photochromic compound is improved. Specifically, in the photochromic compound of the embodiment, the M atom at position 13 is directly bonded to the alkyl group, rather than to the oxygen atom.

[0049] Therefore, the photochromic compound of the embodiment has higher durability than photochromic compounds having substituents introduced via oxygen atoms, such as alkoxy groups.

[0050] As can be seen from the above, if the photochromic compound of the embodiment is used, a photochromic curing composition with excellent solubility in a curing composition is provided, which can achieve cured products and optical articles with excellent durability.

[0051] The following is a detailed description of photochromic compounds having the framework shown in formula (3).

[0052] <m>

[0053] In equation (3), M is C, Si, or Ge. M is preferably C.

[0054] <R 1 >

[0055] R 1 It can be a hydrogen atom or a substituent. If it is a substituent, it can be a group other than a halogen atom or a trifluoromethyl group. In other words, R 1 It can be a substituent other than a halogen atom and a trifluoromethyl group, or a hydrogen atom.

[0056] R 1 Preferably, it is a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a) below, group represented by formula (X) below, or group represented by formula (X3) below.

[0057] R 1 More preferably, it is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3).

[0058] The alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, and even more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0059] The cycloalkyl group is preferably a cycloalkyl group with 3 to 8 carbon atoms (a cycloalkyl group forming a ring with 3 to 8 carbon atoms). Examples of cycloalkyl groups with 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. It should be noted that the cycloalkyl group may have substituents, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms of the substituents.

[0060] The preferred alkoxy group is a substituted or unsubstituted alkoxy group with 1 to 20 carbon atoms, more preferably an unsubstituted alkoxy group with 1 to 10 carbon atoms, and particularly preferably an alkoxy group with 1 to 6 carbon atoms. Examples of suitable alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, etc.

[0061] The amino group can be a primary amino group (-NH2) or a secondary or tertiary amino group in which one or two hydrogen atoms are substituted. Examples of substituents for substituted amino groups include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms. Suitable examples of amino groups include amino, methylamino, dimethylamino, ethylamino, diethylamino, methylphenylamino, and diphenylamino.

[0062] As a heterocyclic group, a heterocyclic group having 3 to 10 atoms is preferred. The heteroatom in the heterocyclic group is preferably at least one selected from the group consisting of oxygen, nitrogen, sulfur, and phosphorus atoms. The number of heteroatoms is, for example, 1 or more and 5 or less, preferably 1 or 2. Specifically, examples include aliphatic heterocyclic groups such as morpholino, piperidinyl, pyrrolyl, piperazine, and N-methylpiperazine, or aromatic heterocyclic groups such as dihydroindolyl. The heterocyclic group can be 2,6-dimethylmorpholino, 2,6-dimethylpiperridinyl, and 2,2,6,6-tetramethylpiperridinyl.

[0063] The alkylthio group is preferably an alkylthio group with 1 to 6 carbon atoms. Examples of alkylthio groups with 1 to 6 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, and tert-butylthio.

[0064] The arylthio group is preferably an arylthio group with 6 to 10 carbon atoms. Examples of arylthio groups with 6 to 10 carbon atoms include phenylthio, 1-naphthio, and 2-naphthio.

[0065] The alkyl carbonyl group is preferably an alkyl carbonyl group with 2 to 7 carbon atoms. Examples of alkyl carbonyl groups with 2 to 7 carbon atoms include acetyl and ethyl carbonyl.

[0066] The alkoxycarbonyl group is preferably an alkoxycarbonyl group with 2 to 7 carbon atoms. Examples of alkoxycarbonyl groups with 2 to 7 carbon atoms include methoxycarbonyl and ethoxycarbonyl.

[0067] Aryl alkyl group is preferably an aryl alkyl group with 7 to 11 carbon atoms. Examples of aryl alkyl groups with 7 to 11 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl.

[0068] The arylalkoxy group is preferably an arylalkoxy group with 7 to 11 carbon atoms. Examples of arylalkoxy groups with 7 to 11 carbon atoms include benzyloxy and naphthylmethoxy.

[0069] The aryloxy group is preferably an aryloxy group with 6 to 12 carbon atoms. Examples of aryloxy groups with 6 to 12 carbon atoms include phenoxy and naphthoxy groups.

[0070] There are no particular restrictions on the aryl group, but it is preferred to be an aryl group with 5 to 12 carbon atoms. Examples of aryl groups with 5 to 12 carbon atoms include phenyl, 1-naphthyl, and 2-naphthyl.

[0071] There are no particular limitations on the heteroaryl group, but it is preferably a heteroaryl group with 3 to 12 carbon atoms. As for the heteroatom, at least one can be selected from the group consisting of oxygen, sulfur, nitrogen, and phosphorus atoms. The number of heteroatoms in the substituted or unsubstituted heteroaryl group is, for example, 1 or more and 3 or less, preferably 1 or 2. The number of carbon atoms in the substituted or unsubstituted heteroaryl group is, for example, 4 or more and 11 or less, preferably 5 or more and 9 or less.

[0072] Examples of heteroaryl groups with 3 to 12 carbon atoms include thienyl, furanyl, pyrrolinyl, pyridinyl, benzothienyl, benzofuranyl, and benzopyrrolinyl.

[0073] The alkoxyalkylthio group is preferably an alkoxyalkylthio group with 2 to 9 carbon atoms. Examples of alkoxyalkylthio groups with 2 to 9 carbon atoms include methoxymethylthio, methoxyethylthio, methoxyn-propylthio, methoxyn-butylthio, ethoxyethylthio, and n-propoxypropylthio.

[0074] The haloalkylthio group is preferably a haloalkylthio group with 1 to 6 carbon atoms. Examples of haloalkylthio groups with 1 to 6 carbon atoms include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio.

[0075] The cycloalkyl thio group is preferably a cycloalkyl thio group with 3 to 8 carbon atoms. Examples of cycloalkyl thio groups with 3 to 8 carbon atoms include cyclopropyl thio, cyclobutyl thio, cyclopentyl thio, and cyclohexyl thio. It should be noted that the cycloalkyl thio group may have substituents, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms of the substituents.

[0076] Silyyl groups may have substituents. There are no particular restrictions on the substituents that can be present in substituted silyl groups, and examples include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0077] Oxymethylsilyl groups may have substituents. There are no particular limitations on the substituents that can be present in substituted oxymethylsilyl groups, and examples include alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 7 carbon atoms, aryl groups with 6 to 14 carbon atoms, and heteroaryl groups with 4 to 14 carbon atoms.

[0078] (The group shown in formula (2a))

[0079] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[0080] In equation (2a), Q 1 It is an alkylene or haloalkylene.

[0081] The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, even more preferably 1 to 7, and most preferably 2 to 6. The halogen atom used as the alkylene haloide can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, more preferably F. In the alkylene haloide, the terminal carbon atom is preferably bonded to the halogen atom, and more preferably the terminal carbon is a perfluoromethyl group.

[0082] Q 2 It is an alkylene or haloalkylene. The preferred method for alkylene or haloalkylene is related to Q. 1 Same. Q 2 The number of carbon atoms in the alkylene or haloalkylene group can be related to Q. 1 The number of carbon atoms in alkylene or haloalkylene compounds can be the same or different.

[0083] Q 3 It can be an alkyl or haloalkyl group, and can be straight-chain or branched, preferably straight-chain.

[0084] The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and most preferably 1 to 7. The halogen atom, as the haloalkyl group, can be at least one selected from the group consisting of I, Cl, Br, and F. The halogen atom is preferably at least one of Cl and F, more preferably F.

[0085] Q 3 Preferably, it is a straight-chain alkyl group.

[0086] X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O). X 1 and X 2 Preferably O, S, or NR 700 The optimal choice is O.

[0087] R 700 and R 701 Each is independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0088] R 700 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0089] R 701 Preferably, it consists of a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The alkyl group is preferably methyl, ethyl, propyl, butyl, or pentyl. The aryl group is preferably phenyl or naphthyl.

[0090] a is 0, or an integer greater than 1 and less than 3.

[0091] Formula (2a) is preferably alkylene alkoxy, alkylene thioalkyl or alkylene oxyalkylene alkoxy.

[0092] In specific examples of equation (2a), we can cite -CH2OCH3, -CH2SCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2SCH3, -CH2CH2CH2OCH3, and -CH2CH2CH2SCH. 3、 -CH2CH2OCH2CH2OCH 3、 And -CH2CH2OCH2CH2OCH2CH3.

[0093] The group represented by formula (2a) is preferably -CH2OCH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -CH2CH2CH2OCH3, -CH2CH2OCH2CH2OCH3, or -CH2CH2OCH2CH2OCH2CH3.

[0094] (The group represented by formula (X))

[0095]

[0096] In equation (X), E is an oxygen atom or NR. 101 R 101 It can be a hydrogen atom or an alkyl group. Preferably, E is NR. 101 And R 101 It is an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0097] F can be an oxygen atom or a sulfur atom. F is preferably an oxygen atom.

[0098] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. G is preferably NH.

[0099] g is 0 or 1.

[0100] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R... 201 It is a group other than a hydrogen atom. R 201 Preferably, it is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0101] The suitable group represented by formula (X) is shown below.

[0102]

[0103] (The group shown in formula (X3))

[0104] L 1 -R 400 (X3)

[0105] In equation (X3),

[0106] R 400 It is a silyl group that is a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or has alkyl, alkoxy or aryl substituents.

[0107] L 1 It is the group represented by the following formula (X2).

[0108]

[0109] In equation (X2), R 30 It is a group represented by the following formula (X2a).

[0110]

[0111] In formulas (X2) and (X2a), J is a divalent group. Each J is independently a directly bonded, substituted, or unsubstituted methylene, oxygen, sulfur, or NR atom. 301 R 301 It can be a hydrogen atom or an alkyl group. R 301 Preferably, the alkyl group has 1 to 20 carbon atoms. The alkyl group is preferably a silyl group, a polymeric group, or a photochromic group having 1 to 10 carbon atoms as a substituent.

[0112] Examples of polymerizable groups include vinyl, 1-chlorovinyl, allyl, styrene, (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, and crotonyl. In addition, epoxy, cyclosulfide, thiocyclobutyl, OH, SH, NH2, COOH, NCO, or NCS groups can also be listed. Preferably, the polymerizable group is selected from at least one group formed by (meth)acryloyl, 2-(methacryloyloxy)ethylcarbamoyl, 2-(methacryloyloxy)ethoxycarbonyl, epoxy, OH, SH, NH2, and COOH groups.

[0113] A photochromic group is a group that contains a photochromic site. Examples of photochromic groups include naphthopyran, spirooxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. From the perspective of exhibiting excellent photochromic properties, indene-naphthopyran is preferred, and indene[2,1-f]naphtho[1,2-b]pyran is particularly preferred.

[0114] The indo[2,1-f]naphtho[1,2-b]pyran is preferably represented by the group shown in the following formula (X4).

[0115]

[0116] In equation (X4), R 401 and R 402 It can be R as shown below 3 and R 4 The same groups are used.

[0117] R 403 and R 404 Each can be independently defined as R as shown below. 3 and R 4 The same groups are used.

[0118] R 405 and R 406 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 405 and R 406 It can be used in conjunction with R described later. 5 and R 6 The same groups are used.

[0119] In equation (X4), o is an integer greater than 0 and less than 4.

[0120] n is an integer greater than 0 and less than 4.

[0121] When o is greater than 2 and less than 4, multiple R 403 Choose either the same or different from each other.

[0122] When n is greater than 2 and less than 4, multiple R 404 Choose either the same or different from each other.

[0123] In R 401 R 402 R 403 R 404 R 405 and R 406 In the case of the group represented by formula (X3), at least one of the substituents on the aryl or heteroaryl group is related to L. 1 Bonding.

[0124] The group represented by the particularly preferred formula (X2) is represented by the following formula.

[0125]

[0126] In formula (X2), L is an oxygen atom or a sulfur atom.

[0127] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents. R 300 Preferably, it is a alkylene group having 1 to 6 carbon atoms or a silylene group having 1 to 6 carbon atoms as a substituent.

[0128] R 302 R 303 and R 304 Each is an alkylene group independently. R 302 Preferably, it is an alkylene group having 1 to 6 carbon atoms. R 303 Preferably, it is an alkylene group having 1 to 6 carbon atoms. R 304 Preferably, it is an alkylene group having 1 to 6 carbon atoms.

[0129] h, j, k, and l are each independently 0 or 1.

[0130] i is an integer greater than or equal to 0 and less than or equal to 200. The structures with multiple i can be the same or different. i is preferably 5 to 100, more preferably 8 to 75, and most preferably a number in the range of 10 to 70.

[0131] In equation (X2), the dashed line represents the intersection with R. 400 The bond.

[0132] <R 2 >

[0133] R 2 It can be a hydrogen atom or a substituent. If it is a substituent, it is a group other than a halogen atom. In other words, R 2 These are substituents other than halogen atoms or hydrogen atoms.

[0134] R 2 Preferably, it is a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group shown in formula (2a), group shown in formula (X), or group shown in formula (X3).

[0135] The haloalkyl group is preferably a haloalkyl group having 1 to 6 carbon atoms. The number of halogen atoms is preferably 1 or more and 10 or less, more preferably 2 or more and 5 or less. As a haloalkyl group having 1 to 6 carbon atoms, it is preferably an alkyl group substituted with fluorine, chlorine or bromine atoms. The haloalkyl group is preferably terminally perfluoromethyl. Examples of preferred haloalkyl groups include trifluoromethyl, trifluoroethyl, trifluoropropyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, bromomethyl, etc.

[0136] As alkyl, cycloalkyl, alkoxy, amino, heterocyclic, alkylthio, arylthio, alkylcarbonyl, alkoxycarbonyl, aralkyl, arylalkoxy, aryloxy, heteroaryl, silyl, oxysilyl, the group shown in formula (2a), the group shown in formula (X), and the group shown in formula (X3), examples of suitable groups include those related to R. 1 The same group is shown in the example.

[0137] <R 3 and R 4 >

[0138] R 3 and R 4 Each is an unsubstituted alkyl group, either linear or branched, with a distinct structure. R 4 The number of carbon atoms in the alkyl group can be greater than or equal to R. 3 The number of carbon atoms in the alkyl group.

[0139] That is, in R 3 In the case of a straight-chain alkyl group, R 4 For more than R carbon atoms 3 Straight-chain alkyl groups, or those with R 3 Branched alkyl groups with the same or more carbon atoms.

[0140] Additionally, in R 3 In the case of a branched alkyl group, R 4 To be with R 3 A straight-chain alkyl group with the same or more carbon atoms. Alternatively, R 4 To have R 3 Branched alkyl groups with the same or more carbon atoms but different structures.

[0141] Furthermore, in R 3 and R 4 When all are branched alkyl groups with 4 or more carbon atoms, as long as R is satisfied... 4 The number of carbons in the alkyl group is greater than or equal to R. 3 The condition of the number of carbon atoms in the alkyl group, then R 3 The main chain can have more carbon atoms than R. 4 The number of carbon atoms in the main chain. In R 3 and R 4 When the main chain has the same number of carbon atoms and the alkyl group has the same number of carbon atoms, the branched alkyl group that is more closely related to the structure of M in formula (3) in terms of substitution position relative to the main chain is taken as R. 3 .

[0142] For example, when the branched alkyl group substituted on M is sec-butyl or isobutyl, the substitution position of the methyl group in the branched chain is closer to that of the sec-butyl group of M, which is R. 3 Isobutyl is R 4 .

[0143] R 3 The preferred number of carbon atoms is 1 to 19, more preferably 1 to 10, further preferably 1 to 9, particularly preferably 1 to 6, and most preferably 1 to 3. A lower number of carbon atoms tends to improve repeated durability. A higher number of carbon atoms tends to improve solubility. 3 Preferably, it is a straight-chain alkyl group.

[0144] In R 3 When the alkyl group is branched, the number of branches is preferably 5 or less, more preferably 3 or less, and more preferably 1.

[0145] The side chain preferably has 5 or fewer carbon atoms, more preferably 3 or fewer, more preferably 2 or fewer, and particularly preferably 1.

[0146] R 4 The preferred number of carbon atoms is 2 to 20, more preferably 2 to 11, further preferably 2 to 10, particularly preferably 2 to 7, and most preferably 2 to 4. A lower number of carbon atoms tends to improve repeated durability. A higher number of carbon atoms tends to improve solubility. 4 Preferably, it is a straight-chain alkyl group.

[0147] From R 4 Subtract R from the number of carbon atoms in the alkyl group 3 The value obtained by subtracting the carbon number of the alkyl group is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, even more preferably 1 or more and 9 or less, further preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1 or more and 2 or less. If the value obtained by subtraction is small, there is a tendency for improved repeated durability. If the value obtained by subtraction is large, there is a tendency for improved solubility.

[0148] As R 3 and R 4 The combination of R is preferred. 3 Alkyl groups with 1 to 19 carbon atoms, whether straight-chain or branched, are R-type alkyl groups. 4 It is an alkyl group with 2 to 20 carbon atoms, either straight or branched, more preferably R. 3 Alkyl groups with 1 to 19 carbon atoms in a straight chain, R 4 It is an alkyl group with 2 to 20 carbon atoms, either straight or branched, with R being more preferred. 3 Alkyl groups with 1 to 19 carbon atoms in a straight chain, R 4 It is a straight-chain alkyl group with 2 to 20 carbon atoms, more preferably R. 3 Alkyl groups with 1 to 9 carbon atoms in a straight chain, R 4 It is a straight-chain alkyl group having 2 to 10 carbon atoms, more preferably R. 3 Alkyl groups with 1 to 6 carbon atoms in a straight chain, R 4 It is a straight-chain alkyl group having 2 to 10 carbon atoms, more preferably R. 3 It is a straight-chain alkyl group with 1 to 3 carbon atoms, R 4 It is a straight-chain alkyl group having 2 to 10 carbon atoms, more preferably R. 3 It is a straight-chain alkyl group with 1 to 3 carbon atoms, R 4 It is a straight-chain alkyl group having 2 to 7 carbon atoms, more preferably R. 3 It is a straight-chain alkyl group with 1 to 3 carbon atoms, R 4 It is an alkyl group with 2 to 4 carbon atoms in a straight chain, with R being the most preferred. 3 and R 4 Either of them is ethyl.

[0149] <R 7 and R 8 >

[0150] R 7 and R 8 Each is an independent substituent.

[0151] b and c are each independently 0, or an integer greater than 1 and less than 3.

[0152] In equation (2), R 7 and R 8 For example, each of the following can be independently a hydroxyl group, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, a substituted or unsubstituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3). As these groups, R can be used. 1 ~R 4 The same group is shown in the example.

[0153] In equation (2), when b is 2~3, multiple R 7 Choose either the same or different from each other.

[0154] In equation (2), for b = 2~3 and there are adjacent R 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 7 The combination represents the 7th and 8th positions of the naphthylpyran skeleton.

[0155] Furthermore, in the existence of R 1 Adjacent R 7 In the case of adjacent R 1 and R 7 The carbon atoms to which they are bonded may optionally form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 1 and R 7 The combination is the 5th and 6th positions, and the 6th and 7th positions of the naphthylpyran skeleton.

[0156] In equation (2), when c is 2~3, multiple R 8 Choose either the same or different from each other.

[0157] In equation (2), for c = 2~3 and there are adjacent R 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 8 The combination represents the 11th and 12th positions of this naphthopyran compound.

[0158] Furthermore, in the existence of R 2 Adjacent R 8 In the case of adjacent R 2 and R 8 The carbon atoms to which they are bonded may optionally form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. As adjacent R 2 and R 8 The combination is at positions 9 and 10, and positions 10 and 11 of the naphthylpyran skeleton.

[0159] It can also contain R 7 Or R 8 The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may have substituents, such as those selected from hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and halogen atoms. Specific examples of these substituents will be described later.

[0160] As R 7 and R 8 A suitable ring that can be formed is the ring shown in the following formula (X5).

[0161]

[0162] In formula (X5), Q and T are each independently a sulfur atom, a substituted or unsubstituted methylene group, an oxygen atom, or an NR atom. 307 The group shown. R 307 It is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, or a group represented by formula (2a).

[0163] R 305 and R 306 Each of the following is preferably an independent hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, substituted amino group, substituted or unsubstituted heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkoxy group, substituted or unsubstituted aryl group, thiol group, alkoxyalkoxy group, haloalkoxy group, cycloalkylthio group, or substituted or unsubstituted arthio group.

[0164] Additionally, R 305 and R 306 The carbon atoms bonded to them can be optionally combined to form substituted or unsubstituted aliphatic rings. Examples of specific aliphatic rings include cyclopentane rings and cyclohexane rings. Furthermore, in this aliphatic ring, 1 to 8 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, can be substituted with at least one group selected from the group consisting of hydroxyl, alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, cyano, nitro, and halogen atoms. Specific examples of these substituents are described later.

[0165] In equation (X5), m is an integer greater than 1 and less than 4.

[0166] <R 5 and R 6 >

[0167] R 5 and R 6 Each can be an independent hydrogen atom or a substituent. As a substituent, R can be used. 1 The substituents are illustrated in equation (3). R is a substituent in equation (3). 5 and R 6 For example, each group can be an substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. These groups can be used with R 1 The same group is shown in the example.

[0168] R 5 and R 6 Each of the following is preferably substituted or unsubstituted: phenyl, substituted or unsubstituted 1-naphthyl, substituted or unsubstituted 2-naphthyl, substituted or unsubstituted thiophene, substituted or unsubstituted furanyl, substituted or unsubstituted pyrrolinyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzofuranyl, or substituted or unsubstituted benzopyrrolinyl. Furthermore, R is preferred. 5 and R 6 At least one of them is a substituted or unsubstituted phenyl, more preferably R 5 and R 6 All are substituted phenyl groups.

[0169] The substituents of the phenyl group are preferably groups represented by formula (2a), hydroxyl, alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or groups represented by formula (X3).

[0170] The substituents present in the phenyl group are more preferably alkyl, haloalkyl, alkoxy, amino, substituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, alkathio, substituted or unsubstituted arylthio, substituted or unsubstituted aryloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkoxyalkathio, haloalkathio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, or groups represented by formula (X3).

[0171] <The photochromic compound shown in formula (4)>

[0172] As suitable photochromic compounds, compounds represented by the following formula (4) can be listed.

[0173] In equation (4), R 1 R 2 R 3 R 4 R 7 R 8 b, c and M each have the same meaning as in equation (3).

[0174]

[0175] <R 9 and R 10 >

[0176] R 9 and R 10 Each of the following is independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3).

[0177] d represents R 9 The number of elements is an integer greater than 0 and less than 5. When d is greater than 2, R... 9 Choose either the same or different from each other.

[0178] In R where d is greater than 2 and less than 5 and there are adjacent values 9 In the case of two adjacent R 9 Optional and bonded to these R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0179] e represents R 10 The number of elements is an integer greater than 0 and less than 5. When e is greater than 2, R... 10 Choose either the same or different from each other.

[0180] In R where e is greater than 2 and less than 5 and there are adjacent values... 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0181] R 9 and R 10 Two adjacent rings can be independently joined to form a cyclic group, optionally comprising at least one of the following groups: oxygen, sulfur, carbon, and nitrogen atoms. The cyclic group is not particularly limited, but preferably contains R. 9 and R 10 The bonded carbon atoms form a ring with 5 to 8 atoms. Furthermore, this ring may also have substituents. Examples of such substituents include hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 3 to 8 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, amino groups, substituted amino groups, heterocyclic groups with 3 to 8 carbon atoms, cyano groups, nitro groups, and substituents from halogen atoms. Specific examples of these substituents can be listed in R. 1 ~R 4 The groups illustrated in the example are the same as the groups described in the example. As R 9 and R 10 The formed ring is preferably formed together with the ring shown in formula (X5).

[0182] <The photochromic compound shown in formula (5)>

[0183] As particularly suitable photochromic compounds, compounds represented by the following formula (5) can be listed. In formula (5), R 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 , d and e each have the same meaning as in equation (4) independently.

[0184]

[0185] <Z 1 and Z 2 >

[0186] Z 1 and Z 2 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3).

[0187] In equation (5), bb represents R. 7 The number of is an integer greater than 0 and less than 2. When bb is 2, R 7 Choose either the same or different from each other. cc represents R. 8 The number of is an integer greater than 0 and less than 2. When cc is 2, R 8 Choose either the same or different from each other.

[0188] Of the photochromic compounds shown in formula (5), R is particularly preferred. 2 The structure is that of a hydrogen atom, i.e., the 10-position is unsubstituted, and R is further preferred. 2 The structure is a hydrogen atom with bb = 0 and cc = 0, which is the structure shown in the following formula (6).

[0189]

[0190] In equation (6), R 1 R 2 R 3 R 4 R 9 R 10 Z 1 Z 2 , d and e each have the same meaning as in equation (5).

[0191] Z 2 Preferably, the group is a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3).

[0192] Z 2 More preferably, it is a hydrogen atom, a substituted or unsubstituted alkyl group, a haloalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a hydroxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkoxyalkyl group. Thio group, haloalkylthio group, substituted or unsubstituted silyl group, group shown in formula (2a), group shown in formula (X), or group shown in formula (X3), more preferably hydrogen atom, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, haloalkylthio group, group shown in formula (2a), or group shown in formula (X3).

[0193] <Detailed explanation of substituents, etc.>

[0194] As mentioned above, R 1 ~R 10 Z 1 and Z 2 The group may have substituents, including hydroxyl, cyano, halogen atom, nitro, formyl, hydroxycarbonyl, thiol, group shown in formula (2a), group shown in formula (X), group shown in formula (X3), alkyl, haloalkyl, cycloalkyl, alkoxy, amino, substituted amino, heterocyclic, halogen atom, alkylthio, arylthio, alkylcarbonyl, alkoxycarbonyl, arylalkyl, arylalkoxy, aryl, heteroaryl, alkoxyalkylthio, haloalkylthio, cycloalkylthio, silyl, or oxysilyl. As these groups, R can be used... 1 ~R 4 The same group as the group detailed in the text.

[0195] <Specific examples of suitable photochromic compounds>

[0196] If a particularly suitable photochromic compound is to be specifically exemplified, the photochromic compound shown in the following formula can be cited.

[0197]

[0198] [Methods for manufacturing photochromic compounds]

[0199] The photochromic compounds of the embodiments can be manufactured by any synthetic method. Representative examples of methods for manufacturing photochromic compounds are described, but the method is not limited to these. It should be noted that, in the following description, unless otherwise specified, the symbols in the formulas have the meanings explained in the above formulas.

[0200] The photochromic compound can be prepared by reacting a naphthol derivative of formula (7) with a propargyl alcohol compound of formula (8) in the presence of an acid catalyst.

[0201]

[0202]

[0203] The reaction ratio of the naphthol derivative to the propargyl alcohol compound is preferably selected from the range of 1:10 to 10:1 (molar ratio). As an acid catalyst, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc., can be used. The acid catalyst is preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the naphthol derivative and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200°C. As a solvent, aprotic organic solvents are preferably used, such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene, etc. The purification method for the product obtained by this reaction is not particularly limited. For example, silica gel column purification can be performed, followed by purification by recrystallization.

[0204] <Synthetic methods of naphthol derivatives>

[0205] Naphthol derivatives can be synthesized using known methods.

[0206] The synthesis method of the naphthol derivative shown in formula (7) is not particularly limited. For example, when M is a carbon atom, it can be synthesized as follows.

[0207] First, by reacting the benzene compound shown in formula (9) with the acyl chloride compound shown in formula (10), the benzophenone compound shown in formula (11) is obtained. It should be noted that in formula (11), R... 1 R 2 R 7 R 8 b and c have the same meaning as in equation (3).

[0208]

[0209]

[0210]

[0211] It should be noted that, depending on the structure and substituents of the photochromic compound to be synthesized, the substituents of the acyl chloride compound and the benzene compound can be interchanged.

[0212] Furthermore, the benzophenone compound (11) is subjected to a Stobbe reaction, a cyclization reaction, a hydrolysis reaction using a base or acid, benzyl protection, or debenzylation based on a hydrolysis reaction using a base or acid, to obtain a carboxylic acid with a hydroxyl group protected by a benzyl group (Bn) as shown in the following formula (12).

[0213]

[0214] Next, the benzyl-protected carboxylic acid shown in formula (12) is converted into an amine by methods such as Curtius rearrangement, Hofmann rearrangement, and Lossen rearrangement, and a diazonium salt is prepared therefrom. The diazonium salt is then converted into halides such as bromide and iodide by Sandmeyer reaction, etc., to obtain the halide shown in formula (13) below (where Hal represents halogen).

[0215]

[0216] The obtained halide is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then reacted with the following formula (14) (where R... 3 and R 4 The ketone (with the same meaning as in formula (3)) is reacted in an organic solvent at -100~70℃ to give the compound shown in formula (15) below.

[0217]

[0218]

[0219] After debenzylation of the compound shown in formula (15), the alcohol is spirocyclized under neutral to acidic conditions at 10 to 120 °C for 10 minutes to 2 hours, thereby synthesizing the naphthol derivative shown in formula (7) as the target. In this reaction, the reaction ratio of the organometallic reagent to the ketone shown in formula (14) is adopted in a wide range, preferably from 1:10 to 10:1 (molar ratio). The reaction temperature is preferably -100 to 70 °C. As a solvent, aprotic organic solvents such as diethyl ether, tetrahydrofuran, benzene, and toluene are preferred. The spirocyclization of the alcohol under neutral to acidic conditions is preferably carried out in the presence of an acid catalyst. As an acid catalyst, acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, and acidic alumina are used for example. Such an acid catalyst is preferably used in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the alcohol. During spirocyclization, it is preferably carried out in the presence of solvents such as tetrahydrofuran, benzene, and toluene.

[0220] <Synthetic methods for naphthol derivatives containing Si and Ge>

[0221] Hereinafter, an example of a method for manufacturing a naphthol derivative in formula (7) where M is Si or Ge will be described.

[0222] First, the halide shown in formula (13) is reacted with magnesium, lithium, etc., to prepare an organometallic reagent. This organometallic reagent is then used in the following formula (16) (where R... 3 and R 4 The monohalides shown in formula (7) are reacted in an organic solvent at -100 to 70°C to give the compounds shown in formula (17).

[0223]

[0224]

[0225] By using the compound shown in formula (17), the cyclized body shown in formula (18) is obtained by a known method.

[0226]

[0227] By debenzylation of the obtained cyclized body, the naphthol derivative shown in formula (7) can be obtained.

[0228] <Specific examples of naphthol derivatives>

[0229] Specific examples of naphthol derivatives include compounds represented by the following formulas.

[0230]

[0231] Identification of Photochromic Compounds

[0232] The photochromic compounds in the embodiments are, for example, solids or viscous liquids at room temperature and pressure. In these solids or liquids, the photochromic compounds can be separated using separation techniques such as thin-layer chromatography, silica gel column chromatography, high-performance liquid chromatography, and gas chromatography. Furthermore, in addition to the photochromic compounds, no byproducts such as starting materials or coloring components have been identified.

[0233] By using proton nuclear magnetic resonance spectroscopy ( 1 Photochromic compounds, as determined by ¹H-NMR, exhibit peaks based on aromatic and alkene protons in the δ range of 5.0–9.0 ppm, and peaks based on alkyl and alkylene protons in the δ range of 1.0–4.0 ppm. Furthermore, by comparing the relative spectral intensities, the number of protons in each bonding group can be determined. This allows for the identification of the skeleton and substituents of the photochromic compounds.

[0234] Furthermore, when the photochromic compound is contained in a cured material such as a resin, the photochromic compound can be separated by dissolving the resin and using the separation method described above.

[0235] <Photochromic Composition>

[0236] The photochromic compound of the embodiment can be dissolved in common organic solvents such as toluene, chloroform, and tetrahydrofuran. When the photochromic compound having the skeleton shown in formula (3) is dissolved in such a solvent, a colorless and transparent solution is obtained. It exhibits a good photochromic effect, rapidly developing color when exposed to sunlight or ultraviolet light, and reversibly and rapidly returning to its original colorless state when sunlight or the like is blocked.

[0237] Furthermore, the photochromic compounds in the embodiments can be used in combination with photochromic compounds having other structures, depending on the intended use. For example, to obtain various hues required for photochromic lenses, they can also be used in combination with other photochromic compounds. Known compounds can be used without any limitations when combining them. Examples include indene-naphthopyran, naphthopyran, spiroxazine, spiropyran, succinic anhydride, succinic imide, and diarylethylene. Among these, indene-naphthopyran compounds are particularly preferred from the viewpoint of uniformly maintaining the hue during color development and fading, suppressing color deviation during color development accompanied by degradation of photochromic properties, and thus reducing initial coloration. In particular, from the perspective of balancing color development concentration at high temperatures and rapid fading rate, as well as excellent durability, it is preferable to use multiple photochromic compounds to adjust the hue.

[0238] When preparing a photochromic composition containing the photochromic compound of the embodiment and other photochromic compounds, the mixing ratio of each photochromic compound can be appropriately determined according to the desired hue.

[0239] <Photochromic Curable Composition>

[0240] The curable composition of the embodiments comprises the photochromic compound of the embodiments; and at least one selected from the group consisting of a free radical polymerizable monomer, a cationic polymerizable monomer, a compound having a polymerization reactive group, and a (thio)carbamate (urea) polymer. Here, the (thio)carbamate (urea) polymer comprises at least one selected from the group consisting of carbamate polymers, thiocarbamate polymers, carbamate urea polymers, and thiocarbamate urea polymers.

[0241] The photochromic compounds and photochromic compositions of the embodiments are preferably combined with polymeric compounds to be used as photochromic curable compositions.

[0242] The photochromic curable composition depends on the color intensity of the photochromic compound, the selected lens material, and the lens thickness; therefore, it cannot be generalized. It is preferable to use the photochromic compound (or photochromic composition) in an amount of 0.001 to 10 parts by weight relative to 100 parts by weight of the polymeric compound. The optimal mixing amount varies depending on the intended use. For example, the following applies to both the use of the photochromic curable composition as a thin film optical article and as a thick film optical article.

[0243] (Use as a thin-film optical article)

[0244] For example, when the photochromic curable composition is made into a film of 10 μm or more and less than 1000 μm, for example, about 100 μm (a polymer film polymerized from the photochromic curable composition), the hue can be adjusted by mixing 0.001 to 10 parts by mass of the photochromic compound (or photochromic composition) of the above embodiment with 100 parts by mass relative to other polymeric monomers.

[0245] (Use as a thick-film optical material)

[0246] In the case of a thick cured material (a polymer molded body formed by polymerizing the photochromic curing composition), for example, a cured material with a thickness of 1 mm or more, the hue can be adjusted by mixing 0.001 to 1 part by mass of the photochromic compound (or photochromic composition) of the above embodiment with 100 parts by mass of the thick cured material or other polymeric monomers that provide the thick cured material.

[0247] <Polymerizing compounds>

[0248] As described above, the photochromic compound is preferably used in combination with a polymerizable compound as a photochromic curable composition. Examples of polymerizable compounds include urethane or urea-based polymeric compounds capable of forming urethane bonds, urea bonds, etc., compounds having polymerizable reactive groups, free radical polymeric compounds, epoxy polymeric compounds, etc. These polymeric compounds are not particularly limited; for example, the polymeric compound described in Patent Document 10 is preferred.

[0249] Among them, the following polymeric compounds are particularly preferred.

[0250] <Compounds with polymerizable reactive groups>

[0251] Examples of compounds having polymerization-reactive groups include compounds having an isocyanate group (isocyanate compounds). An isocyanate compound is a compound having an isocyanate group or an isothiocyanate group, or may contain both an isocyanate group and an isothiocyanate group. This compound is preferably used in combination with compounds containing active hydrogen, as described later. However, this is not a limitation; the following compounds are examples of such isocyanate compounds.

[0252] (Polyisocyanate)

[0253] Polyisocyanates are compounds having at least two isocyanate groups in a single molecule. Examples of polyisocyanates include aromatic polyisocyanates with aromatic rings such as isophthalimide diisocyanate and 4,4'-diphenylmethane diisocyanate, as well as aliphatic polyisocyanates such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0254] (Compounds containing active hydrogen)

[0255] The compounds having active hydrogen are not limited to this, but compounds having hydroxyl and / or thiol groups are preferred, and polyfunctional compounds having two or more active hydrogens in one molecule are particularly preferred. Specifically, examples of compounds having active hydrogen include polyfunctional thiols such as pentaerythritol tetra(3-mercaptopropionate), 4-mercaptomethyl-3,6-dithiooctanedithiol; and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0256] (Free radical polymerizable compounds)

[0257] Radical polymerizable compounds include polyfunctional and monofunctional radical polymerizable compounds. They can be used individually or in combination. Examples of radical polymerizable substituents include groups with unsaturated double bonds, namely vinyl groups (including styryl, (meth)acryloyl, allyl, etc.).

[0258] Polyfunctional radical polymerizable compounds are compounds with two or more radical polymerizable substituents within their molecules. These polyfunctional radical polymerizable compounds include first polyfunctional radical polymerizable compounds with 2 to 10 radical polymerizable substituents and second polyfunctional radical polymerizable compounds with more than 10 radical polymerizable substituents.

[0259] There are no particular limitations on the first type of polyfunctional radical polymerizable compound, but the number of radical polymerizable substituents is more preferably 2 to 6. Specific examples are described below.

[0260] (Polyfunctional (meth)acrylate compounds)

[0261] Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol diglycidyl(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane.

[0262] (Multifunctional allyl compounds)

[0263] Diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chloramphenicol, diallyl hexahydrophthalate, diallyl carbonate, allyl diethylene glycol carbonate, and trimethylolpropane triallyl ester.

[0264] (Polyfunctional thio(meth)acrylate compounds)

[0265] 1,2-bis(methacryloylthio)ethane, bis(2-acryloylthioethyl) ether, 1,4-bis(methacryloylthiomethyl)benzene.

[0266] (Free radical polymerizable compounds)

[0267] Examples of highly functional free radical polymerizable compounds with more than 10 free radical polymerizable substituents include silsesquioxane compounds and polyrotaxane compounds with relatively large molecular weights.

[0268] In addition, a monofunctional free radical polymerizable compound is a compound having a free radical polymerizable substituent in the molecule. However, it is not limited to this specific example, and the following compounds can be cited as examples.

[0269] (Unsaturated carboxylic acids)

[0270] Acrylic acid, methacrylic acid, maleic anhydride.

[0271] ((meth)acrylate)

[0272] Methyl methacrylate, benzyl methacrylate, phenyl methacrylate.

[0273] (Monofunctional (meth)acrylate compounds)

[0274] 2-Hydroxyethyl methacrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyl etheroxymethacrylate, 3-(glycidyl-2-oxyethoxy)-2-hydroxypropyl acrylate, 3-(glycidyl etheroxy-1-isopropyloxy)-2-hydroxypropyl acrylate, 3-glycidyl etheroxy-2-hydroxypropyloxy)-2-hydroxypropyl acrylate.

[0275] (Fumarate)

[0276] Diethyl fumarate, diphenyl fumarate.

[0277] (Thio(meth)acrylic acid)

[0278] Methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate.

[0279] (Vinyl compounds)

[0280] Divinylbenzene, styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene.

[0281] The free radical polymerizable compound can be used alone or in mixtures of multiple compounds. In this case, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set the multifunctional free radical polymerizable compound to 80-100 parts by mass and the monofunctional free radical polymerizable compound to 0-20 parts by mass; more preferably, the multifunctional free radical polymerizable compound to 90-100 parts by mass and the monofunctional free radical polymerizable compound to 0-10 parts by mass. Furthermore, relative to a total of 100 parts by mass of the free radical polymerizable compound, it is preferable to set the first multifunctional free radical polymerizable compound to 80-100 parts by mass, the second multifunctional free radical polymerizable compound to 0-20 parts by mass, and the monofunctional free radical polymerizable compound to 0-20 parts by mass; even more preferably, the first multifunctional free radical polymerizable compound to 85-100 parts by mass, the second multifunctional free radical polymerizable compound to 0-10 parts by mass, and the monofunctional free radical polymerizable compound to 0-10 parts by mass.

[0282] (Various compounding agents)

[0283] In curable compositions, various known compounding agents can be incorporated without impairing the effect. These compounding agents include, for example, release agents, UV absorbers, infrared absorbers, UV stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and various other stabilizers. Additionally, solvents and leveling agents can also be incorporated. Thiols such as tert-dodecyl mercaptan can also be incorporated as polymerization modifiers.

[0284] Among the above-mentioned compounding agents, ultraviolet (UV) stabilizers are preferred from the perspective of improving the durability of photochromic sites. Such UV stabilizers include hindered amine light stabilizers, hindered phenolic antioxidants, and sulfur-based antioxidants. Particularly preferred UV stabilizers are described below.

[0285] Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 manufactured by ADEKA CORPORATION, 2,6-di-tert-butyl-4-methylphenol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] manufactured by BASF Japan Ltd., IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565 manufactured by BASF Japan Ltd. There are no particular restrictions on the amount of such UV stabilizer used, as long as it does not impair the effect. It is usually in the range of 0.001 to 10 parts by weight, especially 0.01 to 1 part by weight, relative to 100 parts by weight of the photochromic curing composition.

[0286] In addition to UV stabilizers, UV absorbers can also be used. Known UV absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, and benzoate compounds can be used as UV absorbers, with cyanoacrylate compounds and benzophenone compounds being particularly preferred. The UV stabilizer is preferably used in the range of 0.001 to 5 parts by weight relative to 100 parts by weight of the photochromic curable composition containing the photochromic compound and the polymerizable compound.

[0287] <Instructions for use of photochromic curable compositions; optical articles>

[0288] Photochromic cured materials are obtained by curing photochromic curable compositions. The polymerization and curing of photochromic cured materials are carried out through free radical polymerization, ring-opening polymerization, anionic polymerization, or polycondensation using active energy rays such as ultraviolet light, alpha rays, beta rays, and gamma rays, heat, or a combination of both. In other words, appropriate polymerization methods are employed depending on the type of polymerizable compound, the type of polymerization accelerator, and the morphology of the resulting photochromic cured material.

[0289] When a curable composition containing polymerizable compounds is thermally polymerized, the temperature affects the properties of the resulting photochromic cured product.

[0290] The temperature conditions are affected by the type and amount of the thermal polymerization initiator and the type of polymerizable compound, so they cannot be generalized. Generally, it is preferable to start polymerization at a relatively low temperature and then slowly increase the temperature. The polymerization time, like the temperature, varies for various reasons, so it is preferable to predetermine the optimal time corresponding to these conditions, but it is generally preferred to select conditions in a way that completes polymerization in 2 to 48 hours. In the case of obtaining photochromic laminates, polymerization is preferably carried out at the temperature at which the polymerizable functional groups react with each other. In this case, the optimal temperature and time are determined in a manner that achieves the target molecular weight.

[0291] Furthermore, during photopolymerization of the curable composition, the polymerization conditions, particularly the UV intensity, affect the properties of the resulting photochromic cured product. These irradiation conditions vary depending on the type and amount of the photopolymerization initiator and the type of polymerizable monomer, and therefore cannot be generalized. Generally, irradiation at a wavelength of 365 nm for 0.5 to 5 minutes at a rate of 50 to 500 mW / cm² is preferred. 2 The selection criteria for UV light mode.

[0292] [Optical Items]

[0293] The photochromic compounds described in this embodiment can be widely used as photochromic materials. For example, they can be used as various storage materials, photocopying materials, photoreceptors for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, photosensitive materials for holography, and other storage materials, replacing silver halide photosensitive materials. Photochromic materials can also be used as photochromic lens materials, optical filter materials, display materials, photometers, decorative materials, etc.

[0294] The photochromic compound described in this embodiment is particularly suitable for use in photochromic lenses. Photochromic lenses are suitable for use as lenses in eyeglasses such as sunglasses. Known methods can be used to manufacture photochromic lenses as long as they achieve uniform light-adjusting performance.

[0295] When photochromic properties are manifested by a mixing method, the above-mentioned curing composition is injected into a glass mold held by an elastomer gasket or spacer. Depending on the type of polymerizable compound and polymerization curing accelerator, a photochromic cured product can be obtained by casting polymerization under heating in an air furnace and irradiation with active energy rays such as ultraviolet light, and can be shaped into an optical material such as a lens.

[0296] In the case of developing photochromic properties through a lamination method, a coating liquid is prepared by appropriately dissolving a curable composition in an organic solvent. The coating liquid is then applied to the surface of an optical substrate such as a lens substrate by spin coating or dipping. After drying to remove the organic solvent, the coating liquid is polymerized and cured by UV irradiation in an inactive gas such as nitrogen or by heating, thereby forming a photochromic layer (coating method) on the surface of the optical substrate.

[0297] Alternatively, by placing an optical substrate such as a lens substrate facing a glass mold in a manner that forms a predetermined gap, and injecting a curable composition into the gap, a photochromic layer formed by the photochromic cured material can be formed on the surface of the optical substrate through casting polymerization based on an inner mold by using UV irradiation, heating, etc. (cast polymerization method).

[0298] When a photochromic layer is formed on the surface of an optical substrate using the lamination method (coating method and casting polymerization method) as described above, the adhesion between the photochromic layer and the optical substrate can be improved by performing pre-treatment on the surface of the optical substrate using chemical treatment based on alkaline solutions, acid solutions, etc., or physical treatment based on corona discharge, plasma discharge, grinding, etc. Alternatively, a transparent adhesive resin layer can be pre-formed on the surface of the optical substrate.

[0299] Furthermore, in the case of exhibiting photochromic properties through an adhesive method, a photochromic sheet is prepared by sheet molding of a curable composition, and then sandwiched between two transparent sheets (optical sheets) and subjected to the aforementioned polymerization and curing, thereby obtaining a photochromic laminate with a photochromic layer as the adhesive layer.

[0300] In this case, the photochromic film can also be produced by coating with a coating solution made by dissolving the curable composition in an organic solvent.

[0301] The photochromic laminate produced in this way is, for example, installed in a mold, and then the optical substrate such as a lens is injection molded with a thermoplastic resin (e.g., polycarbonate) to obtain an optical substrate such as a lens with a specified shape that is endowed with photochromic properties.

[0302] In addition, the photochromic laminate can also be bonded to the surface of an optical substrate using an adhesive or similar agent, thereby obtaining a photochromic lens.

[0303] It should be noted that, when fabricating photochromic laminates as described above, especially from the viewpoint of high adhesion to optical substrates, urethane-based or urea-based polymeric compounds, particularly urethane-based polymeric compounds, are preferably used as polymeric compounds to form polyurethane.

[0304] The above-mentioned curable composition exhibits excellent photochromic properties at high temperature.

[0305] In addition, the photochromic layer and photochromic cured product formed by the curable composition can be dyed with dyes such as disperse dyes, made into hard coating films using hard coating agents with sols as the main components of silane coupling agents, silicon, zirconium, antimony, aluminum, tin, tungsten, etc., formed into thin films based on the vapor deposition of metal oxides such as SiO2, TiO2, ZrO2, and subjected to anti-reflective treatment and antistatic treatment using thin films coated with organic polymers, etc., depending on their application.

[0306] Example

[0307] The present invention will be further described in detail through the following examples. These examples are for illustrative purposes only, and the spirit and scope of the invention are not limited to these examples.

[0308] Example 1

[0309] First process

[0310] Referring to the method described in Patent Document 11, 9.3 g (20.0 mmol) of a halogen compound of formula (1-1) synthesized from 4,4'-dimethylbenzophenone was added to 200 mL of toluene, heated, and 50 mL of toluene was removed by distillation under normal pressure. After distillation, the mixture was cooled to an internal temperature of -20°C, and then 15 mL of n-BuLi (1.6 M hexane solution) was added dropwise while maintaining a temperature below -15°C. After confirming that the raw material was consumed, 2.6 g (30.2 mmol) of methyl propyl ketone was added dropwise while maintaining a temperature below -15°C. After stirring for 1 hour, the temperature was slowly raised to room temperature. 150 mL of water was added, and the mixture was separated. The water washing was repeated until the pH of the aqueous layer reached 7. The resulting organic layer was concentrated and purified by silica gel-based chromatography, thereby obtaining the compound of formula (1-2) in 87% yield.

[0311]

[0312]

[0313] Second process

[0314] 7.12 g (17.4 mmol) of the compound shown in formula (1-2) was dissolved in 75 mL of tetrahydrofuran, and 1.4 g of 5% Pd / C (50% aqueous) was added. The reaction was carried out under pressure of hydrogen at 0.05–0.1 MPa. After confirming that the starting material was consumed, the Pd / C was filtered to remove the solvent from the resulting organic layer, thereby giving the compound shown in formula (1-3) in 100% yield.

[0315]

[0316] Third process

[0317] 5.0 g (26.1 mmol) of p-toluenesulfonic acid monohydrate was added to 100 mL of toluene, and azeotropic dehydration was performed until the water content in the toluene was 92 ppm. After azeotropic dehydration, 5.8 g of the compound shown in formula (1-3) was added, and the mixture was heated at 100 °C. After the starting material was consumed, the mixture was cooled to room temperature, and 48 g of 5% sodium bicarbonate aqueous solution was added. The mixture was stirred and separated. 100 mL of water was added, and the mixture was separated. The washing with water was repeated until the pH of the aqueous layer reached 7. The resulting organic layer was concentrated and purified by silica gel-based chromatography, thereby giving the compound shown in formula (1-4) in 82% yield.

[0318]

[0319] Fourth process

[0320] 3.2 g (10.0 mmol) of the compound shown in formula (1-4) and 3.0 g (12.0 mmol) of propargyl alcohol shown in formula (1-5) were dissolved in 80 mL of toluene, and 0.25 g (1.0 mmol) of pyridinium p-toluenesulfonate was further added. The mixture was stirred at 85 °C for 1 hour. After the compound shown in formula (1-4) was consumed, the mixture was cooled to room temperature, and 80 mL of water was added. The mixture was separated. The solvent of the resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography. Recrystallization using an ethanol / acetonitrile mixture yielded the photochromic compound shown in formula (1-6) in 67% yield.

[0321]

[0322]

[0323] The elemental analysis values ​​of the photochromic compound shown in formula (1-5) are C: 87.24% and H: 6.95%, which are similar to C. 40 H 38 The calculated values ​​for O2, namely C: 87.23% and H: 6.95%, are in good agreement.

[0324] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak based on propyl and methyl 19H in the vicinity of δ0.0~3.5ppm, a peak based on methoxy 3H in the vicinity of δ3.5~5.0ppm, and a peak based on aromatic protons and olefin protons 16H in the vicinity of δ5.0~9.0ppm.

[0325] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0326] (Example 2)

[0327] In the first step of Example 1, 3-methyl-4-methoxybenzophenone was used instead of 4,4'-dimethylbenzophenone, and 3-heptanone was used instead of methylpropyl ketone. In the fifth step, the compound shown in formula (2-1) was used instead of the compound shown in formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (2-2) in 71% yield.

[0328]

[0329]

[0330] The elemental analysis values ​​of the photochromic compound shown in formula (2-2) are C: 82.70% and H: 7.25%, which are similar to C. 44 H 46 The calculated values ​​of O4, namely C: 82.72% and H: 7.26%, are in good agreement.

[0331] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 22H based on methyl, ethyl, butyl, and propoxy groups in the vicinity of δ0.0~3.5ppm, peaks of 8H based on methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and peaks of 16H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0332] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0333] (Example 3)

[0334] In the first step of Example 1, 4,4'-dimethoxybenzophenone was used instead of 4,4'-dimethylbenzophenone, and 4-methyl-3-hexanone was used instead of methylpropyl ketone. In the fifth step, the compound shown in formula (3-1) was used instead of the compound shown in formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (3-2) in a yield of 43%.

[0335]

[0336]

[0337] The elemental analysis values ​​of the photochromic compound shown in formula (3-2) are C: 79.28%, H: 6.95%, N: 2.05%, which are similar to C. 45 H 47 The calculated values ​​of NO5, namely C: 79.27%, H: 6.95%, and N: 2.05%, are in good agreement.

[0338] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 18H based on ethyl, 2-butyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks of 13H based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks of 16H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0339] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0340] (Example 4)

[0341] First process

[0342] Referring to the method described in Patent Document 11, 9.3 g (20.0 mmol) of a carboxylic acid of formula (4-1) synthesized from 3-bromo-4-methoxybenzophenone was synthesized and reacted with 2,6-dimethylbenzylthiol according to the method described in Patent Document 8, thereby obtaining the carboxylic acid compound of formula (4-2) in 92% yield.

[0343]

[0344]

[0345] Second process

[0346] In the first step of Example 1, referring to the method described in Patent Document 11, the iodine compound shown in Formula (4-3) synthesized from the carboxylic acid compound shown in Formula (4-2) was used instead of the compound shown in Formula (1-1), and ethyl propyl ketone was used instead of methyl propyl ketone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in Formula (4-4).

[0347]

[0348]

[0349] Third process

[0350] In the fourth step of Example 1, the compound shown in Formula (4-4) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (3-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (4-5) in 60% yield.

[0351]

[0352] The elemental analysis values ​​of the photochromic compound shown in formula (4-5) are C: 79.14%, H: 6.65%, N: 1.80%, S: 4.14%, which are similar to C. 51 H 51 The calculated values ​​of NO4S, namely C: 79.14%, H: 6.64%, N: 1.81%, and S: 4.14%, are in good agreement.

[0353] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 22H based on methyl, ethyl, propyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a peak of 10H based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a peak of 19H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0354] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0355] (Example 5)

[0356] First process

[0357] In the first step of Example 4, 4-bromo-3',4'-dimethoxybenzophenone was used instead of 4,4'-dimethylbenzophenone, and the reaction was carried out in the same manner to obtain the carboxylic acid compound shown in the following formula (5-1).

[0358]

[0359] Second process

[0360] 24.6 g (49.9 mmol) of the carboxylic acid compound shown in formula (5-1) was mixed with 7.4 g (54.3 mmol) of 4-methylphenylboronic acid, 11.5 g (108.7 mmol) of sodium carbonate, 103.5 mL of water, 121.5 mL of 1,2-dimethoxyethane, and 12.2 mL of ethanol, while stirring under nitrogen bubbling. After bubbling under nitrogen for about 20 minutes, 4142.7 mg (0.1 mmol) of Pd (PPh3)4 was added, and the mixture was reacted at 75 °C for 2 hours. After the reaction, the mixture was cooled to room temperature, 650 mL of THF was added, and the mixture was cooled to 0-5 °C. Concentrated hydrochloric acid was added until pH 1 was reached, and the mixture was separated. The solvent was removed by washing twice with 500 mL of water. Purification was performed by re-slurrying with 300 mL of methanol to obtain the carboxylic acid shown in formula (5-2) in 93% yield.

[0361]

[0362] Third process

[0363] Referring to the method described in Patent Document 11, the iodine compound shown in Formula (5-3) was obtained from the compound shown in Formula (5-2) in a yield of 76%.

[0364]

[0365] Fourth process

[0366] In the first step of Example 1, the compound shown in Formula (1-1) was replaced with Formula (5-3), and methyl butyl ketone was replaced with methyl propyl ketone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in Formula (5-4).

[0367]

[0368] Fifth process

[0369] In the fourth step of Example 1, the compound shown in Formula (5-4) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (5-5) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (5-6) in a yield of 63%.

[0370]

[0371]

[0372] The elemental analysis values ​​of the photochromic compound shown in formula (5-6) are C: 82.04% and H: 6.59%, which are similar to C. 48 H 46 The calculated values ​​of O5, namely C: 82.02% and H: 6.60%, are in good agreement.

[0373] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 15H peak based on methyl and butyl groups in the vicinity of δ0.0~3.5ppm, a 12H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 19H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0374] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0375] (Example 6)

[0376] First process

[0377] Add 6.9 g (15.0 mmol) of the carboxylic acid shown in formula (4-1), 1.6 g (18.0 mmol) of morpholine, 140 mL of toluene, and 5.0 g (45.0 mmol) of potassium tert-butoxide, and stir under reduced pressure to remove dissolved oxygen. Then, add 13.7 mg (0.015 mmol) of Pd2(dba)3 and 28.6 mg (0.06 mmol) of X-phos to the reaction solution and heat to 85°C. Continue heating until the starting material disappears. After the reaction is complete, cool to room temperature and filter. Add 150 mL of tetrahydrofuran and 10% hydrochloric acid to the filtrate, neutralize, and separate. Concentrate the obtained organic layer and then slurry it with 70 mL of 2-propanol for purification, to obtain the carboxylic acid shown in formula (6-1) in 92% yield.

[0378]

[0379] Second process

[0380] In the third step of Example 5, the compound shown in Formula (6-1) was used instead of the compound shown in Formula (5-2), and in the fourth step, 4-octanone was used instead of methyl butyl ketone. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (6-2) in 61% yield.

[0381]

[0382] The elemental analysis values ​​of the photochromic compound shown in formula (6-2) are C: 79.40%, H: 7.10%, N: 2.00%, which are similar to C. 46 H 49 The calculated values ​​of NO5, namely C: 79.39%, H: 7.10%, and N: 2.01%, are in good agreement.

[0383] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on propyl, butyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0384] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0385] (Example 7)

[0386] First process

[0387] 2.75 g (10.0 mmol) of 4-bromo-4'-methylbenzophenone, 1.50 g (14.0 mmol) of N-methylaniline, and 0.29 g (30.0 mol) of sodium tert-butoxide were added to 50 mL of toluene and bubbled under nitrogen for 20 minutes. 46 mg (0.05 mmol) of tris(dibenzylacetone)dipalladium(O) and 95 mg (0.20 mmol) of 2-dicyclohexylphosphine-triisopropylbiphenyl were added, and the mixture was reacted at 80 °C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, and 30 mL of THF was added, followed by filtration. The mixture was cooled at 0–5 °C, and 10% hydrochloric acid was added until the pH reached 6–7. The mixture was separated and washed three times with 100 mL of water. The solvent of the resulting organic layer was removed, and the mixture was purified by silica gel-based chromatography to obtain benzophenone as shown in formula (7-1) in 92% yield.

[0388]

[0389] Second process

[0390] The reaction was carried out according to the method described in Patent Document 12, and propargyl alcohol as shown in the following formula (7-2) was obtained in a yield of 86%.

[0391]

[0392] Third process

[0393] In the first step of Example 1, 4-methoxybenzophenone was used instead of 4,4'-dimethylbenzophenone, and 2-octanone was used instead of methylpropyl ketone. The reaction was carried out in the same manner to synthesize the naphthol compound shown in formula (7-3). 2.5 g (6.7 mmol) of the obtained naphthol compound, 5.0 g of Wakogel C300, and 80 mL of toluene were added, and the mixture was heated to 100°C. 2.85 g (8.7 mmol) of propargyl alcohol (formula (7-2)) dissolved in 20 mL of toluene was added, and the mixture was heated at 100°C. After the naphthol derivative of the starting material was consumed, the mixture was cooled to room temperature and filtered. The solvent of the obtained organic layer was removed, and the mixture was purified by silica gel-based chromatography. Recrystallization using an ethanol / acetonitrile mixture yielded the photochromic compound shown in formula (7-4) in 58% yield.

[0394]

[0395]

[0396] The elemental analysis values ​​of the photochromic compound shown in formula (7-4) are C: 86.05%, H: 7.21%, N: 2.06%, which are similar to C. 49 H 49 The calculated values ​​of NO2, namely C: 86.05%, H: 7.22%, and N: 2.05%, are in good agreement.

[0397] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 24H peak based on methyl, ethyl, and hexyl groups in the vicinity of δ0.0~3.5ppm, a 3H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 22H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0398] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0399] (Example 8)

[0400] First process

[0401] In the first step of Example 5, 4-bromo-4'-methoxybenzophenone was used instead of 4-bromo-3',4'-dimethoxybenzophenone, and the reaction was carried out in the same manner to obtain the carboxylic acid compound shown in the following formula (8-1).

[0402]

[0403] Second process

[0404] In the first step of Example 7, the compound shown in formula (7-1) was used instead of 4-bromo-4'-methylbenzophenone, and diphenylamine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to synthesize the carboxylic acid shown in formula (8-2) in 91% yield.

[0405]

[0406] Third process

[0407] In the third step of Example 5, the compound shown in Formula (7-2) was used instead of the compound shown in Formula (5-2), and in the fourth step, 4-nonanone was used instead of methyl butyl ketone. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (7-3) in 57% yield.

[0408]

[0409] The elemental analysis values ​​of the photochromic compound shown in formula (8-3) are C: 83.42%, H: 6.76%, and N: 1.78%, which are similar to C. 55 H 53 The calculated values ​​of NO4, namely C: 83.41%, H: 6.74%, and N: 1.77%, are in good agreement.

[0410] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak based on propyl and pentyl 18H in the vicinity of δ0.0~3.5ppm, a peak based on methoxy 9H in the vicinity of δ3.5~5.0ppm, and a peak based on aromatic protons and olefin protons 26H in the vicinity of δ5.0~9.0ppm.

[0411] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0412] (Example 9)

[0413] In the first step of Example 6, N-methylaniline was used instead of morpholine, and in the second step, methyl ethyl ketone was used instead of 4-octanone. Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (9-1) in a yield of 66%.

[0414]

[0415] The elemental analysis values ​​of the photochromic compound shown in formula (9-1) are C: 81.92%, H: 6.26%, N: 2.11%, which are similar to C. 45 H 51 The calculated values ​​of NO4, namely C: 81.91%, H: 6.26%, and N: 2.12%, are in good agreement.

[0416] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl and ethyl protons in the vicinity of δ0.0~3.5ppm, peaks based on methoxy protons in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0417] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0418] (Example 10)

[0419] In the first step of Example 5, 3-bromo-4-methoxy-4'-methylbenzophenone was used instead of 4-bromo-3,4'-dimethoxybenzophenone; in the second step, 4-morpholinophenylboronic acid was used instead of 4-methylphenylboronic acid; in the fourth step, 4-octanone was used instead of methyl butyl ketone; and in the fifth step, the compound shown in formula (3-1) was used instead of the compound shown in formula (5-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (10-1) in 56% yield.

[0420]

[0421] The elemental analysis values ​​of the photochromic compound shown in formula (10-1) are C: 79.99%, H: 7.17%, N: 3.34%, which are similar to C. 56 H 60 The calculated values ​​of N2O5, namely C: 79.97%, H: 7.19%, and N: 3.33%, are in good agreement.

[0422] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 27H based on methyl, propyl, butyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a peak of 14H based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a peak of 19H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0423] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0424] (Example 11)

[0425] In Example 10, 3-bromo-4-methoxy-4'-bromobenzophenone was used instead of 3-bromo-4-methoxy-4'-methylbenzophenone, excess 4-isopropoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid, 3-nonanone was used instead of 4-octanone, and the compound shown in formula (2-1) was used instead of the compound shown in formula (3-1). The reaction was carried out in the same manner otherwise to obtain the photochromic compound shown in formula (11-1) in 54% yield.

[0426]

[0427] The elemental analysis values ​​of the photochromic compound shown in formula (11-1) are C: 82.16%, H: 7.43%, and N: 3.34%, which are similar to C. 56 H 60 The calculated values ​​of N2O5, namely C: 82.14% and H: 7.44%, are in good agreement.

[0428] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 35H based on ethyl, hexyl, isopropoxy, and propoxy in the vicinity of δ0.0~3.5ppm, a peak of 10H based on methoxy, isopropoxy, and propoxy in the vicinity of δ3.5~5.0ppm, and a peak of 23H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0429] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0430] (Example 12)

[0431] First process

[0432] In the first step of Example 7, 4-bromo-4'-methoxybenzophenone was used instead of 4-bromo-4'-methylbenzophenone, and diphenylamine was used instead of N-methylaniline. Otherwise, the reaction was carried out in the same manner to synthesize propargyl alcohol as shown in the following formula (12-1).

[0433]

[0434] Second process

[0435] In Example 10, 3-bromo-4,4'-dimethylbenzophenone was used instead of 3-bromo-4-methoxy-4'-methylbenzophenone, 4-methoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid, ethylpropyl ketone was used instead of 4-octanone, and the compound shown in formula (12-1) was used instead of the compound shown in formula (3-1). The reaction was carried out in the same manner to obtain the photochromic compound shown in formula (12-2) in 62% yield.

[0436]

[0437] The elemental analysis values ​​of the photochromic compound shown in formula (12-2) are C: 86.01%, H: 6.46%, N: 1.71%, which are similar to C. 58 H 51 The calculated values ​​of NO3, namely C: 85.99%, H: 6.48%, and N: 1.70%, are in good agreement.

[0438] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, ethyl, and propyl 18H in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino 6H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons 29H in the vicinity of δ5.0~9.0ppm.

[0439] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0440] (Example 13)

[0441] First process

[0442] In the first step of Example 12, N-methylaniline was used instead of diphenylamine, and the reaction was carried out in the same manner to synthesize propargyl alcohol as shown in the following formula (13-1).

[0443]

[0444] Second process

[0445] In Example 10, 3-bromo-4-methoxybenzophenone was used instead of 3-bromo-4-methoxy-4'-methylbenzophenone, 2,4-dimethoxyphenylboronic acid was used instead of 4-morpholinophenylboronic acid, methyl ethyl ketone was used instead of 4-octanone, and the compound shown in formula (13-1) was used instead of the compound shown in formula (3-1). The reaction was carried out in the same manner otherwise to obtain the photochromic compound shown in formula (13-2) in 56% yield.

[0446]

[0447] The elemental analysis values ​​of the photochromic compound shown in formula (13-2) are C: 81.56%, H: 6.17%, N: 1.82%, which are similar to C. 52 H 47 The calculated values ​​of NO5, namely C: 81.54%, H: 6.19%, and N: 1.83%, are in good agreement.

[0448] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 11H based on methyl and ethyl groups in the vicinity of δ0.0~3.5ppm, peaks of 12H based on methoxy groups in the vicinity of δ3.5~5.0ppm, and peaks of 24H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0449] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0450] (Example 14)

[0451] In the second step of Example 6, ethylpropyl ketone was used instead of 4-octanone, and the reaction was carried out in the same manner to obtain the photochromic compound shown in the following formula (14-1) in a yield of 64%.

[0452]

[0453] The elemental analysis values ​​of the photochromic compound shown in formula (14-1) are C: 79.12%, H: 6.77%, N: 2.11%, which are similar to C. 44 H 45 The calculated values ​​of NO5, namely C: 79.13%, H: 6.79%, and N: 2.10%, are in good agreement.

[0454] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on ethyl, propyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0455] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0456] (Example 15)

[0457] In the first step of Example 1, 4-methoxy-4'-trifluoromethoxybenzophenone was used instead of 4,4'-dimethylbenzophenone, and 3-octanone was used instead of methylpropyl ketone. In the fourth step, the compound shown in formula (5-5) was used instead of the compound shown in formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (15-1) in 65% yield.

[0458]

[0459] The elemental analysis values ​​of the photochromic compound shown in formula (15-1) are C: 74.31% and H: 5.93%, which are similar to C. 43 H 41 The calculated values ​​of F3O5, namely C: 74.33% and H: 5.95%, are in good agreement.

[0460] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on ethyl and pentyl 16H in the vicinity of δ0.0~3.5ppm, peaks based on methoxy 9H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0461] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0462] (Example 16)

[0463] In the first step of Example 6, 1,2,3,4-tetrahydroquinoline was used instead of morpholine, and in the second step, 5-decanone was used instead of 4-octanone, and the compound shown in formula (2-1) was used instead of the compound shown in formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in formula (16-1) in 61% yield.

[0464]

[0465] The elemental analysis values ​​of the photochromic compound shown in formula (16-1) are C: 82.79%, H: 7.44%, N: 1.76%, which are similar to C. 55 H 59 The calculated values ​​of NO4, namely C: 82.77%, H: 7.45%, and N: 1.76%, are in good agreement.

[0466] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 31H peak based on butyl, pentyl, propoxy, and 1,2,3,4-tetrahydroquinoline cyclogroups in the vicinity of δ0.0~3.5ppm, an 8H peak based on methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and a 20H peak based on aromatic protons and alkene protons in the vicinity of δ5.0~9.0ppm.

[0467] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0468] (Example 17)

[0469] First process

[0470] Referring to the method described in Patent Document 8, 3-bromoanisole is reacted with 4'-(1,1-dimethylethyl)[1,1'-biphenyl]-4-carboxyl chloride to obtain benzophenone as shown in the following formula (17-1) in 88% yield.

[0471]

[0472] Second process

[0473] In Example 6, benzophenone of Formula (17-1) was used instead of 3-bromo-4-methoxybenzophenone, piperidine was used instead of morpholine, and 3-heptanone was used instead of 4-octanone. The reaction was carried out in the same manner otherwise, to obtain the photochromic compound of Formula (17-2) in 53% yield.

[0474]

[0475] The elemental analysis values ​​of the photochromic compound shown in formula (17-2) are C: 82.80%, H: 7.58%, N: 1.72%, which are similar to C. 56 H 61 The calculated values ​​of NO4, namely C: 82.82%, H: 7.57%, and N: 1.72%, are in good agreement.

[0476] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 33H peak based on ethyl, butyl, tert-butyl, and piperidinyl groups in the vicinity of δ0.0~3.5ppm, a 9H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 19H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0477] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0478] (Example 18)

[0479] In the second step of Example 6, 3-nonanone was used instead of 4-octanone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (18-1) in 58% yield.

[0480]

[0481] The elemental analysis values ​​of the photochromic compound shown in formula (18-1) are C: 79.50%, H: 7.23%, N: 1.98%, which are similar to C. 47 H 51 The calculated values ​​of NO5, namely C: 79.52%, H: 7.24%, and N: 1.97%, are in good agreement.

[0482] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 22H peak based on ethyl, hexyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a 13H peak based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a 16H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0483] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0484] (Example 19)

[0485] In the second step of Example 6, 2-tetaneone was used instead of 4-octanone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (19-1) in a yield of 49%.

[0486]

[0487] The elemental analysis values ​​of the photochromic compound shown in formula (19-1) are C: 79.99%, H: 7.74%, N: 1.84%, which are similar to C. 51 H 59 The calculated values ​​of NO5, namely C: 79.96%, H: 7.76%, and N: 1.83%, are in good agreement.

[0488] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 30H peak based on methyl, undecyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a 13H peak based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a 16H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0489] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0490] (Example 20)

[0491] In the second step of Example 6, 3-methyl-4-octanone was used instead of 4-octanone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (20-1) in 51% yield.

[0492]

[0493] The elemental analysis values ​​of the photochromic compound shown in formula (20-1) are C: 79.54%, H: 7.24%, N: 1.96%, which are similar to C. 47 H 51 The calculated values ​​of NO5, namely C: 79.52%, H: 7.24%, and N: 1.97%, are in good agreement.

[0494] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 22H peak based on 2-methylpropyl, butyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a 13H peak based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a 16H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0495] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0496] (Evaluation of the physical properties of photochromic plastic lenses produced by coating method)

[0497] (Example 21)

[0498] (Preparation of curable composition)

[0499] First, the photochromic compound, photopolymerization initiator, and polymerizable compound obtained in Example 1 above are mixed to obtain a curable composition.

[0500] As a polymerizable compound, a polymerizable compound is used that is formulated by combining the following free radical polymerizable monomers.

[0501] Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by weight

[0502] Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by weight

[0503] Trimethylolpropane trimethacrylate: 38 parts by weight

[0504] γ-Methacryloxypropyltrimethoxysilane: 2 parts by weight

[0505] Glycidyl methacrylate: 1 part by weight

[0506] It should be noted that when the total amount of free radical polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.25mmol.

[0507] The following additives are used as additives.

[0508] Phenylacetylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad 819): 0.3 parts by weight)

[0509] Ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (stabilizer, Irganox 245: 1 part by weight)

[0510] bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate: 3 parts by weight

[0511] DuPont Toray Specialty Materials KK leveling agent (L-7001): 0.1 parts by weight

[0512] It should be noted that the above additives are the mixing ratio when the total amount of free radical polymerizable monomers is set to 100 parts by mass.

[0513] (Manufacturing of optical items)

[0514] Using this curable composition, polymerization is carried out as follows to obtain a photochromic laminate based on a lamination method.

[0515] First, a thiocarbamate-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as the optical substrate. It should be noted that the thiocarbamate-based plastic lens was first subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and then thoroughly cleaned with distilled water.

[0516] Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was applied to the surface of the aforementioned plastic lens at a speed of 70 rpm for 15 seconds, followed by a 10-second application at 1000 rpm. Then, approximately 2 g of the aforementioned photochromic curing composition was spin-coated at 60 rpm for 40 seconds, followed by a 10-20 second application at 600 rpm, resulting in a photochromic coating layer thickness of 40 μm.

[0517] A lens with a photochromic curable composition (photochromic coating) coated on its surface was used in a nitrogen atmosphere with an output power of 200mW / cm. 2 The coating is cured by irradiating it with a metal halide lamp for 90 seconds. Then, it is further heated at 110°C for 1 hour to produce a photochromic laminate with a photochromic layer.

[0518] (Examples 22-40)

[0519] Photochromic laminates were fabricated using the photochromic compounds obtained in Examples 2-20, following the same method as in Example 21.

[0520] (Comparative Examples 1-4)

[0521] Using the photochromic compounds shown in formulas (A) to (D) below, each photochromic laminate was obtained in the same manner as in Example 21.

[0522]

[0523]

[0524]

[0525]

[0526] (Synthesis of compound A)

[0527] In the second step of Example 6, acetone was used instead of 4-octanone, and the reaction was carried out in the same manner to synthesize compound (A).

[0528] (Synthesis of compound C)

[0529] Compound (C) is synthesized by reacting the compound of the following formula (C-1) synthesized by the method described in Patent Document 13 with tris(trimethylsiloxane)silylethylchlorosilane by the method described in Patent Document 3.

[0530]

[0531] (Synthesis of compound D)

[0532] In the second step of Example 6, cyclooctanone was used instead of 4-octanone, and the reaction was carried out in the same manner to synthesize compound (D).

[0533] <Evaluation Methods>

[0534] The obtained photochromic laminate was evaluated using the method shown below.

[0535] (1) Photochromic properties

[0536] [1] Maximum absorption wavelength (λmax):

[0537] The maximum absorption wavelength after color development was determined using a spectrophotometer (MCPD3000 instantaneous multichannel photodetector) manufactured by OTSUKA ELECTRONICS CO.,LTD, and used as an indicator of hue during color development.

[0538] [2] Colorimetric concentration at 23℃ (A) 23 ):

[0539] The difference between the absorbance {ε(240)} after 240 seconds of light irradiation at 23°C at the maximum absorption wavelength and the absorbance ε(0) before irradiation is used as an indicator of colorimetric concentration. The higher this value, the better the photochromic property.

[0540] [3] Fading half-life at 23℃ [τ1 / 2 (sec.)]:

[0541] The time required for the absorbance of the sample at its maximum absorption wavelength to decrease to half of {ε(240)-ε(0)} after 240 seconds of light irradiation at 23°C and then stopping the light irradiation is used as an indicator of the fading rate. The shorter this time, the faster the fading rate.

[0542] [4] Residual rate (A) 96 / A0×100): The photochromic plastic lens was subjected to accelerated degradation for 96 hours using a xenon lamp weathering tester (X25) manufactured by Suga Test Instruments Co., Ltd. Then, the colorimetric concentration was evaluated before and after the test, measuring the colorimetric concentration before the test (A0) and the colorimetric concentration after the test (A100). 96 ), compare it with (A) 96 / A0) is used as the residue rate, which serves as an indicator of the durability of the color development. The higher the residue rate, the higher the durability of the color development.

[0543] The results of Examples 26, 34, 38-40 and Comparative Examples 1-4 are summarized in Table 1, and the results of Examples 21-25, 27-33 and 35-37 are summarized in Table 2.

[0544] [Table 1]

[0545]

[0546] [Table 2]

[0547]

[0548] <Property Evaluation of Photochromic Layers Fabricated Using Adhesive Method>

[0549] (Example 41)

[0550] The adhesive sheet is manufactured using the following method. The adhesive sheet is made by sequentially stacking a first optical sheet, a first adhesive layer, a photochromic layer, a second adhesive layer, and a second optical sheet. A polycarbonate sheet with a thickness of 400 μm is used as both the first and second optical sheets.

[0551] (Preparation of the composition for forming a photochromic layer)

[0552] In a 2L four-necked flask equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe, 315 parts by mass of polycarbonate diol with a number average molecular weight of 1000, 100 parts by mass of isophorone diisocyanate, and 72 parts by mass of toluene were added. The mixture was reacted at 100°C for 7 hours under a nitrogen atmosphere to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was complete, the reaction solution was cooled to near 0°C and dissolved in 205 parts by mass of tert-butanol and 382 parts by mass of diethyl ketone, and the liquid temperature was maintained at 0°C. Then, a mixed solution of 21.3 parts by mass of bis(4-aminocyclohexyl)methane and 20 parts by mass of diethyl ketone as a chain extender was added dropwise over 30 minutes, and the reaction was carried out at 0°C for 1 hour. Then, 8.1 parts by mass of 1,2,2,6,6-pentamethyl-4-aminopiperidine were added dropwise, and the mixture was reacted at 0°C for 1 hour to obtain a diethyl ketone solution of terminal non-reactive carbamate urea resin.

[0553] 100 parts by weight of the obtained terminal non-reactive carbamate urea resin solution, 6.3 parts by weight of the photochromic compound shown in Example 1 (a mixture of isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (polyisocyanate compound)), 0.4 parts by weight of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] as an antioxidant, and 0.06 parts by weight of DuPont Toray Specialty Materials KK L-7001 as a surfactant were added and stirred and mixed at room temperature to obtain a composition for forming a photochromic layer.

[0554] In addition, a photochromic compound is added in a manner that yields 0.25 mmol per 100 parts by weight of terminal non-reactive urethane resin.

[0555] (Preparation of the adhesive layer composition)

[0556] A 5L separable flask (4-necked) equipped with a stirring blade, cooling pipe, thermometer, and nitrogen inlet pipe was prepared. 400 parts by mass of polycarbonate diol (number average molecular weight 1000), 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were added to the flask. The reaction was carried out under a nitrogen atmosphere at 110°C for 7 hours to synthesize a urethane prepolymer with isocyanate groups at the ends. After the urethane prepolymer reaction was completed, the reaction solution was cooled to approximately 20°C and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, and the liquid temperature was maintained at 20°C. Next, 60 parts by mass of isophorone diamine as a chain extender were added dropwise, and the reaction was carried out at 20°C for 1 hour. Then, 3 parts by mass of n-butylamine were further added dropwise, and the reaction was carried out at 20°C for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a terminally non-reactive urethane urea resin.

[0557] Add 0.2 parts by mass of DuPont Toray Specialty Materials KK L-7001 as a surfactant to 500 parts by mass of the obtained terminal non-reactive urethane resin solution, and stir and mix at room temperature to obtain a composition for adhesive layer.

[0558] (Manufacturing of adhesive sheets)

[0559] Using a coating machine (manufactured by TESTER SANGYO CO,. LTD.), the adhesive layer composition was coated onto one main surface of the first optical film at a coating speed of 0.5 m / min, and dried at a drying temperature of 110°C for 3 minutes, thereby obtaining a first optical film with a first coating film thickness of 5 μm. Using the same method, the adhesive layer composition was coated onto one main surface of the second optical film to obtain a second optical film with a second coating film.

[0560] Next, using a coating machine (manufactured by TESTER SANGYO CO,. LTD.), the photochromic layer forming composition was coated onto a 50 μm thick OPP film (stretched polypropylene film) at a coating speed of 0.3 m / min, and dried at a drying temperature of 100°C for 5 minutes. This yielded a third coating. Then, the third coating was bonded to the first optical sheet in contact with the first coating. The OPP film was peeled off from the structure, and the second optical sheet and the third coating were bonded together with the exposed main surface of the third coating in contact with the second coating. The resulting laminate was then left to stand at 40°C under vacuum for 24 hours, followed by heat treatment at 110°C for 60 minutes, then humidified at 60°C and 100% RH for 24 hours, and finally left to stand at 40°C under vacuum for 24 hours to obtain an adhesive sheet. The obtained adhesive sheet was evaluated in the same manner as in Example 21. The results are shown in Table 3.

[0561] (Examples 42-53, Comparative Examples 5 and 6)

[0562] Adhesive sheets were prepared using the photochromic compounds shown in Table 3, following the same method as in Example 41.

[0563] [Table 3]

[0564]

[0565] <Physical Property Evaluation of Photochromic Cured Products Produced by Mixing Method>

[0566] (Example 54)

[0567] (Preparation of curable composition)

[0568] First, the photochromic compound, additive, and polymerizable compound obtained in Example 1 are mixed to obtain a curable composition. As the polymerizable compound, a polymerizable compound formulated by combining the following polymerizable monomers is used.

[0569] · 1,3-bis(isocyanate methyl)cyclohexane: 36.7 parts by weight

[0570] • Pentaerythritol tetra(3-mercaptopropionate): 39.4 parts by weight

[0571] • Polyoxyethylene polyoxypropylene lauryl ether (manufactured by AOKI OIL INDUSTRIAL Co., Ltd., WANDERSURF140): 17.4 parts by weight

[0572] ·1-Decanthiol: 2.8 parts by weight

[0573] • RX-1 prepared using the method described in Patent Document 14: 3.8 parts by weight

[0574] It should be noted that when the total amount of polymerizable monomers in the curable composition is set to 100g, the photochromic compound is added in a manner that results in 0.106mmol.

[0575] The following additives are used as additives.

[0576] • Dimethyltin dichloride: 0.05 parts by weight

[0577] • Irganox 245: 0.1 parts by weight

[0578] · 2-Ethylhexyl 4-methoxycinnamic acid: 0.6 parts by weight

[0579] (Manufacturing of solidified products)

[0580] After thorough degassing, the prepared curable composition was injected into a glass mold with a 1 mm gap, and polymerization was carried out by casting. Polymerization was performed in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured material was removed from the glass mold, yielding a 1 mm thick photochromic cured product. The obtained photochromic cured product was evaluated in the same manner as in Example 23. The results are shown in Table 4.

[0581] (Examples 55-66, Comparative Examples 7 and 8)

[0582] Photochromic cured products were prepared using the photochromic compounds shown in Table 4, following the same method as in Example 50. The results are summarized in Table 4.

[0583] [Table 4]

[0584]

[0585] <Solubility Evaluation of Photochromic Compounds>

[0586] The photochromic compounds of the examples and comparative examples shown in Table 5 were used to evaluate their solubility in polymeric compounds.

[0587] Specifically, in the curable composition used in Example 21, a photochromic compound was added to a composition containing only a free radical polymerizable compound to prepare a sample. The concentration of the photochromic compound was set at 35 μmol / g.

[0588] It should be noted that the experiment was conducted using the "Yokai-kun USS-1" manufactured by Nippon Seiki Co., Ltd., under the following conditions.

[0589] Dissolution temperature: 65-70℃

[0590] Mixing conditions: Mixing disc 5.

[0591] Ultrasonic irradiation conditions: irradiation interval of 3 seconds.

[0592] Dissolution confirmation was performed every 15 minutes until 1 hour later. Light was then passed through the sample for visual confirmation. The degree of dissolution was evaluated using the following four levels of evaluation criteria.

[0593] (Evaluation Criteria)

[0594] 1: Even when light was passed through for confirmation, no turbidity was observed, indicating complete dissolution.

[0595] 2: A very faint turbidity was observed, which could be confirmed by allowing light to pass through.

[0596] 3: A slight turbidity was observed that allowed light to pass through, which could be confirmed by observation.

[0597] 4: The degree of turbidity can be confirmed even without allowing light to pass through.

[0598] A shorter time required to achieve an evaluation result of 1 indicates higher solubility. The evaluation results for solubility are shown in Table 5.

[0599] [Table 5]

[0600]

[0601] Example 72

[0602] First process

[0603] 36.0 g (73.0 mmol) of carboxylic acid as shown in formula (5-1) was mixed with 27.4 g (211.7 mmol) of N-ethyldiisopropylamine and 360 mL of toluene. The mixture was stirred under reduced pressure to remove dissolved oxygen. Then, 34.5 g (4.9 mmol) of Pd2(dba) and 5.7 g (9.8 mmol) of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthrene were added to the reaction mixture. After stirring at room temperature for 30 minutes, the mixture was heated to an internal temperature of 70 °C. 25.1 g (141.1 mmol) of 3-trifluoromethylbenzenethiol was slowly added dropwise. After each addition, the mixture was heated until reflux was reached. Heating continued until the starting material disappeared. After the reaction was completed and cooled to room temperature, 540 mL of tetrahydrofuran was added. 360 mL of water was then added, and the mixture was separated. This process was repeated three times. The solvent was removed from the organic layer, and the mixture was purified by silica gel-based chromatography to give the carboxylic acid shown in the following formula (72-1) in 56% yield.

[0604]

[0605] Second process

[0606] In the third step of Example 5, the carboxylic acid shown in Formula (72-1) is used instead of the carboxylic acid shown in Formula (5-2), and in the fourth step, ethyl propyl ketone is used instead of methyl butyl ketone. Otherwise, the reaction is carried out in the same manner to synthesize the naphthol compound shown in Formula (72-2).

[0607]

[0608] Third process

[0609] In the fourth step of Example 1, the compound shown in Formula (72-2) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (2-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (72-3) in a yield of 63%.

[0610]

[0611] The elemental analysis values ​​of the photochromic compound shown in formula (72-3) are C: 73.50%, H: 5.78%, and S: 3.91%, which are similar to C. 50 H 47 The calculated values ​​of F3O5S, namely C: 73.51%, H: 5.80%, and S: 3.92%, are well consistent.

[0612] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 17H peak based on ethyl, propyl, and propoxy groups in the vicinity of δ0.0~3.5ppm, an 11H peak based on methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and a 19H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0613] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0614] Example 73

[0615] First process

[0616] In the second step of Example 8, the carboxylic acid shown in Formula (72-1) was used instead of the carboxylic acid shown in Formula (8-1), and N-methylaniline was used instead of diphenylamine. In the third step, methyl butyl ketone was used instead of 4-nonanone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in Formula (73-1).

[0617]

[0618] Second process

[0619] In the fourth step of Example 1, the compound shown in Formula (73-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (2-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (73-2) in 68% yield.

[0620]

[0621] The elemental analysis values ​​of the photochromic compound shown in formula (73-2) are C: 80.51%, H: 6.91%, N: 1.90%, which are similar to C. 50 H 51 The calculated values ​​of NO5, namely C: 80.51%, H: 6.89%, and N: 1.88%, are in good agreement.

[0622] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, butyl, and propoxy 20H in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and propoxy 11H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons 20H in the vicinity of δ5.0~9.0ppm.

[0623] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0624] Example 74

[0625] First process

[0626] In the first step of Example 4, 3-bromo-4,4'-dimethoxybenzophenone was used instead of 3-bromo-4-methoxybenzophenone, and in the second step, methyl ethyl ketone was used instead of ethyl propyl ketone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (74-1).

[0627]

[0628] Second process

[0629] In the fourth step of Example 1, the compound shown in Formula (74-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (3-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (74-2) in 68% yield.

[0630]

[0631] The elemental analysis values ​​of the photochromic compound shown in formula (74-2) are C: 77.40%, H: 6.36%, N: 1.82%, S: 4.11%, which are similar to C. 50 H 49 The calculated values ​​of NO5S, namely C: 77.39%, H: 6.36%, N: 1.81%, and S: 4.13%, are in good agreement.

[0632] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl, ethyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0633] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0634] Example 75

[0635] First process

[0636] In the first step of Example 8, 4-bromo-3-methyl-4'-methoxybenzophenone was used instead of 4-bromo-4'-methoxybenzophenone; in the second step, benzomorpholine was used instead of diphenylamine; and in the third step, methyl ethyl ketone was used instead of 4-nonanone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (75-1).

[0637]

[0638] Second process

[0639] In the fourth step of Example 1, the compound shown in Formula (75-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (2-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (75-2) in a yield of 67%.

[0640]

[0641] The elemental analysis values ​​of the photochromic compound shown in formula (75-2) are C: 80.63%, H: 6.51%, N: 1.91%, which are similar to C. 49 H 47 The calculated values ​​of NO5, namely C: 80.63%, H: 6.49%, and N: 1.92%, are in good agreement.

[0642] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 18H based on methyl, ethyl, benzylmorpholino, and propoxy groups in the vicinity of δ0.0~3.5ppm, peaks of 10H based on methoxy and benzylmorpholino groups in the vicinity of δ3.5~5.0ppm, and peaks of 19H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0643] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0644] Example 76

[0645] First process

[0646] In the first step of Example 10, 3-bromo-4-methoxybenzophenone was used instead of 3-bromo-4-methoxy-4'-methylbenzophenone, 4-chlorophenylboronic acid was used instead of 4-morpholinophenylboronic acid, and ethyl butyl ketone was used instead of 4-octanone. The reaction was carried out in the same manner to synthesize the compound shown in the following formula (76-1).

[0647]

[0648] Second process

[0649] In the first step of Example 6, the compound represented by formula (76-1) was used instead of the carboxylic acid represented by formula (4-1), and diphenylamine was used instead of morpholine; otherwise, the reaction was carried out in the same manner. After the reaction was completed, water was added, and the mixture was separated and washed repeatedly with water until the pH of the aqueous layer reached 7. After concentrating the obtained organic layer, it was purified by silica gel-based chromatography, thereby obtaining the compound represented by formula (76-2) in 94% yield.

[0650]

[0651] Third process

[0652] In the second step of Example 1, the compound shown in formula (76-2) was used instead of the compound shown in formula (1-2), and the reaction was carried out in the same manner to synthesize the naphthol compound shown in formula (76-3).

[0653]

[0654] Fourth process

[0655] In the first step of Example 17, 3-fluoro-4-propoxybenzene was used instead of 3-bromoanisole, and 4-bromobenzoyl chloride was used instead of 4'-(1,1-dimethylethyl)[1,1'-biphenyl]-4-carboxyl chloride. Otherwise, the reaction was carried out in the same manner to synthesize benzophenone as shown in the following formula (76-4).

[0656]

[0657] Fifth process

[0658] In the first step of Example 12, benzophenone of formula (76-4) was used instead of 4-bromo-4'-methoxybenzophenone, and N-methylaniline was used instead of diphenylamine. Otherwise, the reaction was carried out in the same manner to synthesize propargyl alcohol of formula (76-5).

[0659]

[0660] Sixth process

[0661] In the fourth step of Example 1, the compound shown in Formula (76-3) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (76-5) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (76-6) in a yield of 64%.

[0662]

[0663] The elemental analysis values ​​of the photochromic compound shown in formula (76-6) are C: 83.69%, H: 6.41%, and N: 2.91%, which are similar to C. 67 H 61 The calculated values ​​of FN2O3, namely C: 83.72%, H: 6.40%, and N: 2.91%, are in good agreement.

[0664] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 22H based on methyl, ethyl, butyl, and propoxy in the vicinity of δ0.0~3.5ppm, a peak of 5H based on methoxy and propoxy in the vicinity of δ3.5~5.0ppm, and a peak of 34H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0665] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0666] Example 77

[0667] First process

[0668] In the first step of Example 74, ethyl butyl ketone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (77-1) in a yield of 60%.

[0669]

[0670] The elemental analysis values ​​of the photochromic compound shown in formula (77-1) are C: 83.69%, H: 6.41%, N: 2.91%, S: 3.92%, which are similar to C. 53 H 55 The calculated values ​​of NO5S, namely C: 77.81%, H: 6.78%, N: 1.71%, and S: 3.92%, are in good agreement.

[0671] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 24H based on methyl, ethyl, butyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks of 13H based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks of 18H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0672] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0673] Example 78

[0674] First process

[0675] In the second step of Example 13, 2,4,6-trimethoxyphenylboronic acid was used instead of 2,4-dimethoxyphenylboronic acid, and ethylpropyl ketone was used instead of methyl ethyl ketone. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (78-1).

[0676]

[0677] Second process

[0678] In the fourth step of Example 1, the compound shown in Formula (78-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (12-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (78-2) in 68% yield.

[0679]

[0680] The elemental analysis values ​​of the photochromic compound shown in formula (78-2) are C: 81.35%, H: 6.25%, N: 1.56%, which are similar to C. 60 H 55 The calculated values ​​of NO6, namely C: 81.33%, H: 6.26%, and N: 1.58%, are in good agreement.

[0681] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 12H peak based on ethyl and propyl groups in the vicinity of δ0.0~3.5ppm, a 15H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 28H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0682] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0683] Example 79

[0684] First process

[0685] In Example 10, ethylpropyl ketone was used instead of 4-octanone, and the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (79-1).

[0686]

[0687] Second process

[0688] In the fourth step of Example 1, the compound shown in Formula (79-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (3-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (79-2) in a yield of 60%.

[0689]

[0690] The elemental analysis values ​​of the photochromic compound shown in formula (79-2) are C: 79.79%, H: 6.93%, N: 3.48%, which are similar to C. 54 H 56 The calculated values ​​of N2O5, namely C: 79.77%, H: 6.94%, and N: 3.45%, are in good agreement.

[0691] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks of 23H based on methyl, ethyl, propyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks of 14H based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks of 19H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0692] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0693] Example 80

[0694] First process

[0695] In Example 9, ethyl butyl ketone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (80-1).

[0696]

[0697] Second process

[0698] In the fourth step of Example 1, the compound shown in Formula (80-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (5-5) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (80-2) in a yield of 60%.

[0699]

[0700] The elemental analysis values ​​of the photochromic compound shown in formula (80-2) are C: 82.15%, H: 6.77%, N: 1.99%, which are similar to C. 48 H 47 The calculated values ​​of NO4, namely C: 82.14%, H: 6.75%, and N: 2.00%, are in good agreement.

[0701] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 17H peak based on methyl, ethyl, and butyl protons in the vicinity of δ0.0~3.5ppm, a 9H peak based on methoxy protons in the vicinity of δ3.5~5.0ppm, and a 21H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0702] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0703] Example 81

[0704] First process

[0705] In the first step of Example 76, 2-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid, and in the second step, morpholine was used instead of diphenylamine. Otherwise, the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (81-1).

[0706]

[0707] Second process

[0708] In the fourth step of Example 1, the compound shown in Formula (81-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (5-5) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (81-2) in a yield of 68%.

[0709]

[0710] The elemental analysis values ​​of the photochromic compound shown in formula (81-2) are C: 80.83%, H: 6.77%, N: 1.85%, which are similar to C. 51 H 51 The calculated values ​​of NO5, namely C: 80.82%, H: 6.78%, and N: 1.85%, are in good agreement.

[0711] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on ethyl, butyl, and morpholino groups of 18H in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino groups of 13H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons of 20H in the vicinity of δ5.0~9.0ppm.

[0712] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0713] Example 82

[0714] First process

[0715] In the first step of Example 73, ethyl butyl ketone was used instead of methyl butyl ketone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (82-1) in a yield of 71%.

[0716]

[0717] The elemental analysis values ​​of the photochromic compound shown in formula (82-1) are C: 80.63%, H: 7.01%, N: 1.85%, which are similar to C. 51 H 53 The calculated values ​​of NO5, namely C: 80.60%, H: 7.03%, and N: 1.84%, are in good agreement.

[0718] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 22H based on methyl, ethyl, butyl, and propoxy in the vicinity of δ0.0~3.5ppm, a peak of 11H based on methoxy and propoxy in the vicinity of δ3.5~5.0ppm, and a peak of 20H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0719] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0720] Example 83

[0721] First process

[0722] In Example 9, ethylpropyl ketone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner to synthesize the naphthol compound shown in the following formula (83-1).

[0723]

[0724] Second process

[0725] In the fourth step of Example 1, the compound shown in Formula (83-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (12-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (83-2) in 68% yield.

[0726]

[0727] The elemental analysis values ​​of the photochromic compound shown in formula (83-2) are C: 84.43%, H: 6.33%, N: 3.39%, which are similar to C. 58 H 52 The calculated values ​​of N2O3, namely C: 84.43%, H: 6.35%, and N: 3.40%, are in good agreement.

[0728] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 15H peak based on methyl, ethyl, and propyl groups in the vicinity of δ0.0~3.5ppm, a 6H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 31H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0729] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0730] Example 84

[0731] In the fourth step of Example 1, the compound shown in Formula (79-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (7-2) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (84-1) in 56% yield.

[0732]

[0733] The elemental analysis values ​​of the photochromic compound shown in formula (84-1) are C: 83.79%, H: 6.93%, N: 3.44%, which are similar to C. 57 H 56 The calculated values ​​of N2O3, namely C: 83.79%, H: 6.91%, and N: 3.43%, are in good agreement.

[0734] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on 25H of methyl, ethyl, propyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks based on 7H of methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks based on 24H of aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0735] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0736] Example 85

[0737] In the first step of Example 74, butylhexyl ketone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (85-1) in 55% yield.

[0738]

[0739] The elemental analysis values ​​of the photochromic compound shown in formula (85-1) are C: 78.30%, H: 7.28%, N: 1.59%, S: 3.66%, which are similar to C. 57 H 63 The calculated values ​​of NO5S, namely C: 78.31%, H: 7.26%, N: 1.60%, and S: 3.67%, are in good agreement.

[0740] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 32H peak based on methyl, butyl, hexyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, a 13H peak based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and a 18H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0741] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0742] Example 86

[0743] In the second step of Example 13, the compound shown in formula (76-5) was used instead of the compound shown in formula (13-1), and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in formula (86-1) in a yield of 63%.

[0744]

[0745] The elemental analysis values ​​of the photochromic compound shown in formula (86-1) are C: 79.86%, H: 6.20%, N: 1.72%, which are similar to C. 54 H 50 The calculated values ​​of FNO5, namely C: 79.88%, H: 6.21%, and N: 1.73%, are in good agreement.

[0746] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 16H peak based on methyl, ethyl, and propoxy groups in the vicinity of δ0.0~3.5ppm, an 11H peak based on methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and a 23H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0747] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0748] Example 87

[0749] First process

[0750] In the first step of Example 73, ethyl propyl ketone was used instead of methyl butyl ketone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (87-1) in a yield of 72%.

[0751]

[0752] The elemental analysis values ​​of the photochromic compound shown in formula (87-1) are C: 80.53%, H: 6.89%, N: 1.88%, which are similar to C. 50 H 51 The calculated values ​​of NO5, namely C: 80.51%, H: 6.89%, and N: 1.88%, are in good agreement.

[0753] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on 20H of methyl, ethyl, propyl, and propoxy groups in the vicinity of δ0.0~3.5ppm, peaks based on 11H of methoxy and propoxy groups in the vicinity of δ3.5~5.0ppm, and peaks based on 20H of aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0754] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0755] Example 88

[0756] First process

[0757] In the first step of Example 4, the carboxylic acid compound represented by formula (8-1) was used instead of the carboxylic acid represented by formula (4-1), and the reaction was carried out in the same manner to synthesize the naphthol compound represented by formula (88-1).

[0758]

[0759] Second process

[0760] In the fourth step of Example 1, the compound shown in Formula (88-1) was used instead of the compound shown in Formula (1-4), and the compound shown in Formula (13-1) was used instead of the compound shown in Formula (1-5). Otherwise, the reaction was carried out in the same manner to obtain the photochromic compound shown in Formula (88-2) in a yield of 61%.

[0761]

[0762] The elemental analysis values ​​of the photochromic compound shown in formula (88-2) are C: 81.69%, H: 6.45%, N: 1.77%, S: 4.02%, which are similar to C. 54 H 51 The calculated values ​​of NO3S, namely C: 81.68%, H: 6.47%, N: 1.76%, and S: 4.04%, are in good agreement.

[0763] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a peak of 21H based on methyl, ethyl, and propyl groups in the vicinity of δ0.0~3.5ppm, a peak of 6H based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a peak of 24H based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0764] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0765] Example 89

[0766] In the first step of Example 78, methyl propyl ketone was used instead of ethyl propyl ketone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (89-1) in a yield of 63%.

[0767]

[0768] The elemental analysis values ​​of the photochromic compound shown in formula (89-1) are C: 81.24%, H: 6.16%, N: 1.60%, which are similar to C. 59 H 53 The calculated values ​​of NO6, namely C: 81.26%, H: 6.13%, and N: 1.61%, are in good agreement.

[0769] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed a 10H peak based on methyl and propyl groups in the vicinity of δ0.0~3.5ppm, a 15H peak based on methoxy groups in the vicinity of δ3.5~5.0ppm, and a 28H peak based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0770] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0771] Example 90

[0772] In Example 15, 2-heptanone was used instead of 3-octanone, and the reaction was carried out in the same manner otherwise, to give the photochromic compound shown in the following formula (90-1) in 62% yield.

[0773]

[0774] The elemental analysis values ​​of the photochromic compound shown in formula (90-1) are C: 74.30% and H: 5.93%, which are similar to C. 43 H 41 The calculated values ​​of F3O5, namely C: 74.33% and H: 5.95%, are in good agreement.

[0775] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on methyl and hexyl 16H in the vicinity of δ0.0~3.5ppm, peaks based on methoxy 9H in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0776] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0777] Example 91

[0778] In Example 3, ethylpropyl ketone was used instead of 4-methyl-3-hexanone, and the reaction was carried out in the same manner otherwise, to obtain the photochromic compound shown in the following formula (91-1) in 67% yield.

[0779]

[0780] The elemental analysis values ​​of the photochromic compound shown in formula (91-1) are C: 79.14%, H: 6.81%, N: 2.09%, which are similar to C. 44 H 45 The calculated values ​​of NO5, namely C: 79.13%, H: 6.79%, and N: 2.10%, are in good agreement.

[0781] In addition, proton nuclear magnetic resonance spectroscopy was measured, and the results showed peaks based on ethyl, propyl, and morpholino groups in the vicinity of δ0.0~3.5ppm, peaks based on methoxy and morpholino groups in the vicinity of δ3.5~5.0ppm, and peaks based on aromatic protons and olefin protons in the vicinity of δ5.0~9.0ppm.

[0782] Furthermore, measurement 13 C-NMR spectroscopy results show peaks for aromatic ring-based carbons near δ110–160 ppm, peaks for olefin-based carbons near δ80–140 ppm, and peaks for alkyl-based carbons near δ20–60 ppm.

[0783] Examples 92-111

[0784] Photochromic laminates were prepared using the photochromic compounds obtained in Examples 72-91, following the same method as in Example 21.

[0785] The evaluation results are summarized in Tables 6 and 7.

[0786] [Table 6]

[0787]

[0788] [Table 7]

[0789]

[0790] (Examples 112-127, Comparative Examples 13-20)

[0791] The solubility in polymerizable compounds was evaluated using the photochromic compounds of the examples and comparative examples shown in Tables 8 to 14, following the same method as in Example 67.

[0792] It should be noted that in Comparative Examples 13 to 20, the photochromic compounds shown in the following formulas (E) to (L) were used to evaluate their solubility in polymeric compounds.

[0793] (Synthesis of the compound shown in formula (E))

[0794] In Example 3, 3,3,5,5-tetramethylcyclohexanone was used instead of 4-methyl-3-hexanone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (E).

[0795]

[0796] (Synthesis of the compound shown in formula (F))

[0797] In Example 9, diethyl ketone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (F).

[0798]

[0799] (Synthesis of the compound shown in formula (G))

[0800] In Example 9, acetone was used instead of 4-octanone, and the reaction was carried out in the same manner to synthesize the compound shown in formula (G) below.

[0801]

[0802] (Synthesis of the compound represented by formula (H))

[0803] In Example 15, acetone was used instead of 3-octanone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (H).

[0804]

[0805] (Synthesis of the compound shown in formula (I))

[0806] In Example 73, acetone was used instead of methyl butyl ketone, and the reaction was carried out in the same manner to synthesize the compound shown in Formula (I).

[0807]

[0808] (Synthesis of the compound represented by formula (J))

[0809] In Example 74, 4,4-diethylcyclohexanone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (J).

[0810]

[0811] (Synthesis of the compound represented by formula (K))

[0812] In Example 74, acetone was used instead of methyl ethyl ketone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (K).

[0813]

[0814] (Synthesis of the compound represented by formula (L))

[0815] In Example 78, acetone was used instead of ethyl propyl ketone, and the reaction was carried out in the same manner to synthesize the compound shown in the following formula (L).

[0816]

[0817] [Table 8]

[0818]

[0819] [Table 9]

[0820]

[0821] [Table 10]

[0822]

[0823] [Table 11]

[0824]

[0825] [Table 12]

[0826]

[0827] [Table 13]

[0828]

[0829] [Table 14]

[0830]

[0831] The following notes are preferred embodiments of this disclosure. [1]

[0833] A photochromic compound having the framework shown in formula (3) below:

[0834]

[0835] In the above formula (1),

[0836] M is C, Si, or Ge.

[0837] R 1 It can be a hydrogen atom or a substituent; if it is a substituent, it cannot be a halogen atom or a trifluoromethyl group.

[0838] R 2 It can be a hydrogen atom or a substituent; if it is a substituent, it is not a halogen atom.

[0839] R 3 and R 4 Each is an alkyl group that is either straight-chain or branched, and has a different structure from the others.

[0840] R 5 and R 6 Each can be an independent hydrogen atom or a substituent.

[0841] R 7 and R 8 Each is an independent substituent.

[0842] b and c are each an independent integer greater than or equal to 0 and less than or equal to 3. [2]

[0844] According to the photochromic compound described in [1], wherein, in the formula (3), R 3 R is an alkyl group with 1 to 19 carbon atoms, either straight or branched. 4 Alkyl groups with 2 to 20 carbon atoms, either straight or branched, from R 4 Subtract R from the number of carbon atoms in the alkyl group 3 The value is obtained by determining the number of carbon atoms in the alkyl group, which is greater than or equal to 1 and less than 10. [3]

[0846] According to the photochromic compound described in [1] or [2], wherein, in the formula (3), R 3 It is a straight-chain alkyl group with 1 to 10 carbon atoms. [4]

[0848] According to any one of [1] to [3], the photochromic compound, wherein, in the formula (3), R 3 R is a straight-chain alkyl group with 1 to 9 carbon atoms. 4 It is a straight-chain alkyl group with 2 to 10 carbon atoms, from R 4 Subtract R from the number of carbon atoms in the alkyl group 3 The value is obtained by determining the number of carbon atoms in the alkyl group, which is greater than or equal to 1 and less than or equal to 9. [5]

[0850] The photochromic compound according to any one of [1] to [4], wherein, in the formula (3), R 3 It is any one of methyl, ethyl, or propyl. [6]

[0852] According to any one of [1] to [5], the photochromic compound, wherein, in the formula (3), R 3 and R 4 Either of them is ethyl. [7]

[0854] The photochromic compound according to any one of [1] to [6], wherein, in the formula (3), R 7 and R 8 Each of the following groups is independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3).

[0855] In the above formula (3),

[0856] When b is 2~3, multiple R 7 Choose either the same or different.

[0857] When c is 2~3, multiple R 8 Choose either the same or different.

[0858] In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0859] In R where c is 2~3 and there are adjacent values 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0860] -Q 1 -(X) 1 Q 2 )aX 2 Q 3 (2a)

[0861] In the above formula (2a),

[0862] Q 1 It is an alkylene or haloalkylene.

[0863] Q 2 It is an alkylene or haloalkylene.

[0864] Q 3 It is an alkyl or haloalkyl group.

[0865] X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O),

[0866] R 700 and R 701 Each of these can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0867] a is an integer that is 0, or greater than 1 and less than 3.

[0868] L 1 -R 400 (X3)

[0869] In the above formula (X3),

[0870] R 400 It is a silyl group consisting of a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or having alkyl, alkoxy, or aryl substituents.

[0871] L 1 The group is represented by the following formula (X2).

[0872]

[0873] In the above equation (X2), R 30 The group is represented by the following formula (X2a).

[0874]

[0875] In equations (X2) and (X2a),

[0876] J is a divalent group, which can be independently a directly bonded, substituted, or unsubstituted methylene group, oxygen atom, sulfur atom, or NR group. 301 R 301 It is a hydrogen atom or an alkyl group.

[0877] L represents an oxygen atom or a sulfur atom.

[0878] R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents.

[0879] R 302 R 303 and R 304 Each is independently an alkylene group.

[0880] h, j, k, and l are each independently 0 or 1.

[0881] If i is an integer greater than or equal to 0 and less than 200, then when i is greater than or equal to 2, multiple R... 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond,

[0882]

[0883] In the above formula (X),

[0884] E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group.

[0885] F represents an oxygen atom or a sulfur atom.

[0886] G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0887] g is 0 or 1.

[0888] R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl.

[0889] When G is an oxygen atom or a sulfur atom, R 201 It refers to groups other than hydrogen atoms. [8]

[0891] According to any one of [1] to [7], in the photochromic compound, R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. [9]

[0893] The photochromic compound according to any one of [1] to [8] is represented by the following formula (4):

[0894]

[0895] In the above equation (4),

[0896] R 1 R 2 R 3 R 4 R 7 R 8 b, c, and M each have the same meaning as in equation (3).

[0897] R 9 and R 10 Each of the following groups is independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3).

[0898] d is an integer greater than 0 and less than 5.

[0899] When d is 2~5, multiple R 9 Choose either the same or different.

[0900] In the case of adjacent R 9 In the case of two adjacent R 9 Optional and bonded to R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[0901] e is an integer greater than 0 and less than 5.

[0902] When e is 2~5, multiple R 10 Choose either the same or different.

[0903] In the case of adjacent R 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

[10]

[0905] According to any one of [1] to [9], the photochromic compound, wherein, in the formula (3), R 1 The following groups are included: hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3).

[0906] R 2 The group can be a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), the group represented by formula (X), or the group represented by formula (X3).

[11]

[0908] According to any one of [1] to

[10] , the photochromic compound, wherein, in the formula (3), R 1 The group can be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3).

[12]

[0910] The photochromic compound according to any one of [1] to

[11] is represented by the following formula (5):

[0911]

[0912] In the above equation (5),

[0913] R 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 , d, and e each have the same meaning as in equation (4).

[0914] Z 1 and Z 2 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3).

[0915] bb is an integer greater than 0 and less than 2, cc is an integer greater than 0 and less than 2.

[0916] When bb is 2, multiple R 7 Choose either the same or different.

[0917] With cc = 2, multiple R 8 Choose either the same or different from each other.

[13]

[0919] According to the photochromic compound described in

[12] , wherein, in the formula (5), R 2 For hydrogen atoms, bb = 0 and cc = 0.

[14]

[0921] According to the photochromic compound described in

[12] or

[13] , wherein, in the formula (5), Z 2 The group can be a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), the group represented by formula (X), or the group represented by formula (X3).

[15]

[0923] A curable composition comprising: the photochromic compound described in any one of [1] to

[14] ; and

[0924] Select at least one from the group consisting of free radical polymerizable monomers, cationic polymerizable monomers, compounds having polymerizable reactive groups, and (thio)carbamate (urea) polymers.

[16]

[0926] A cured product, which is a cured product of the curable composition described in

[15] .

[17]

[0928] An optical article comprising the cured material described in

[16] .

[18]

[0930] A lens comprising any one of the photochromic compounds described in [1] to

[14] .

[19]

[0932] A pair of eyeglasses comprising the lens described in

[18] .< / m>

Claims

1. A photochromic compound represented by the following formula (3), In the above formula (3), M is C, Si, or Ge. R 1 It can be a hydrogen atom or a substituent; if it is a substituent, it cannot be a halogen atom or a trifluoromethyl group. R 2 It can be a hydrogen atom or a substituent; if it is a substituent, it is not a halogen atom. R 3 and R 4 Each is an alkyl group that is either straight-chain or branched, and has a different structure from the others. R 5 and R 6 Each can be an independent hydrogen atom or a substituent. R 7 and R 8 Each is an independent substituent. b and c are each independently 0, or an integer greater than 1 and less than 3.

2. The photochromic compound according to claim 1, wherein, In the above equation (3), R 3 R is an alkyl group with 1 to 19 carbon atoms, either straight or branched. 4 Alkyl groups with 2 to 20 carbon atoms, either straight or branched, from R 4 Subtract R from the number of carbon atoms in the alkyl group 3 The value is obtained by determining the number of carbon atoms in the alkyl group, which is greater than or equal to 1 and less than 10.

3. The photochromic compound according to claim 1, wherein, In the above equation (3), R 3 It is a straight-chain alkyl group with 1 to 10 carbon atoms.

4. The photochromic compound according to claim 1, wherein, In the above equation (3), R 3 R is a straight-chain alkyl group with 1 to 9 carbon atoms. 4 It is a straight-chain alkyl group with 2 to 10 carbon atoms, from R 4 Subtract R from the number of carbon atoms in the alkyl group 3 The value is obtained by determining the number of carbon atoms in the alkyl group, which is greater than or equal to 1 and less than or equal to 9.

5. The photochromic compound according to claim 1, wherein, In the above equation (3), R 3 It can be any one of methyl, ethyl, or propyl.

6. The photochromic compound according to claim 1, wherein, In the above equation (3), R 3 and R 4 Either of them is ethyl.

7. The photochromic compound according to claim 1, wherein, In the above equation (3), R 7 and R 8 Each of the following groups is independently hydroxyl, substituted or unsubstituted alkyl, haloalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic, cyano, halogen atom, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, nitro, formyl, hydroxycarbonyl, substituted or unsubstituted alkylcarbonyl, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, thiol, substituted or unsubstituted alkoxyalkylthio, haloalkylthio, substituted or unsubstituted cycloalkylthio, substituted or unsubstituted silyl, substituted or unsubstituted oxysilyl, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3). In the above formula (3), When b is 2~3, multiple R 7 Choose either the same or different. When c is 2~3, multiple R 8 Choose either the same or different. In R where b is 2~3 and there are adjacent values 7 In the case of two adjacent R 7 Optional and bonded to R 7 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. In R where c is 2~3 and there are adjacent values 8 In the case of two adjacent R 8 Optional and bonded to R 8 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. -Q 1 -(X 1 Q 2 )a-X 2 Q 3 (2a) In the above formula (2a), Q 1 It is an alkylene or haloalkylene. Q 2 It is an alkylene or haloalkylene. Q 3 It is an alkyl or haloalkyl group. X 1 and X 2 Each is independently O, S, NR 700 PR 701 Or P (=O), R 700 and R 701 Each of these can be independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or substituted aryl group, or a substituted or unsubstituted heteroaryl group. a is an integer that is 0, or greater than 1 and less than 3. L 1 -R 400 (X3) In the above formula (X3), R 400 It is a silyl group consisting of a hydrogen atom, alkyl group, aryl group, polymeric group, photochromic group, or having alkyl, alkoxy, or aryl substituents. L 1 The group is represented by the following formula (X2). In the above equation (X2), R 30 The group is represented by the following formula (X2a). In equations (X2) and (X2a), J represents a divalent group, which can be independently a directly bonded, substituted or unsubstituted methylene group, an oxygen atom, a sulfur atom, or an NR group. 301 R 301 It is a hydrogen atom or an alkyl group. L represents an oxygen atom or a sulfur atom. R 300 It is an alkylene group or a silylene group having alkyl or aryl substituents. R 302 R 303 and R 304 Each is independently an alkylene group. h, j, k, and l are each independently 0 or 1. If i is an integer greater than or equal to 0 and less than 200, then when i is greater than or equal to 2, multiple R... 30 Choose either the same or different; the dashed line indicates the same as R. 400 The bond, In the above formula (X), E represents an oxygen atom or NR. 101 R 101 It is a hydrogen atom or an alkyl group. F represents an oxygen atom or a sulfur atom. G represents an oxygen atom, a sulfur atom, or NR. 202 R 202 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. g is 0 or 1. R 201 It can be a hydrogen atom, alkyl, cycloalkyl, aryl, or heteroaryl. When G is an oxygen atom or a sulfur atom, R 201 It refers to groups other than hydrogen atoms.

8. The photochromic compound according to claim 1, wherein, In the above equation (3), R 5 and R 6 Each can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

9. The photochromic compound according to claim 7, which is represented by the following formula (4), In the above equation (4), R 1 R 2 R 3 R 4 R 7 R 8 b, c, and M each have the same meaning as in equation (3). R 9 and R 10 Each of the following groups is independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a nitro group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), or a group represented by formula (X3). d is an integer greater than 0 and less than 5. When d is 2~5, multiple R 9 Choose either the same or different. In the case of adjacent R 9 In the case of two adjacent R 9 Optional and bonded to R 9 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings. e is an integer greater than 0 and less than 5. When e is 2~5, multiple R 10 Choose either the same or different. In the case of adjacent R 10 In the case of two adjacent R 10 Optional and bonded to R 10 The carbon atoms together form substituted or unsubstituted aliphatic rings, substituted or unsubstituted aliphatic heterocycles, substituted or unsubstituted aromatic rings, substituted or unsubstituted aromatic heterocycles, or substituted or unsubstituted fused polycyclic rings with aromatic rings or aromatic heterocycles fused to these rings.

10. The photochromic compound according to claim 7, wherein, In the above equation (3), R 1 The following groups are included: hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3). R 2 The group can be a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), the group represented by formula (X), or the group represented by formula (X3).

11. The photochromic compound according to claim 7, wherein, In the above equation (3), R 1 The group can be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a cyano group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxyalkylthio group, a haloalkylthio group, a substituted or unsubstituted cycloalkylthio group, a substituted or unsubstituted silyl group, a substituted or unsubstituted oxysilyl group, a group represented by formula (2a), a group represented by formula (X), or a group represented by formula (X3).

12. The photochromic compound according to claim 9, which is represented by the following formula (5), In the above equation (5), R 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 , d, and e each have the same meaning as in equation (4). Z 1 and Z 2 Each of the following is independently a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, group represented by formula (2a), group represented by formula (X), or group represented by formula (X3). bb is an integer greater than 0 and less than 2, cc is an integer greater than 0 and less than 2. When bb = 2, multiple R 7 Choose either the same or different. With cc = 2, multiple R 8 Choose either the same or different from each other.

13. The photochromic compound according to claim 12, wherein, In equation (5), R 2 For hydrogen atoms, bb = 0 and cc = 0.

14. The photochromic compound according to claim 12, wherein, In the above equation (5), Z 2 The group can be a hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group, haloalkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, cyano group, halogen atom, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, thiol group, substituted or unsubstituted alkoxyalkylthio group, haloalkylthio group, substituted or unsubstituted cycloalkylthio group, substituted or unsubstituted silyl group, substituted or unsubstituted oxysilyl group, the group represented by formula (2a), the group represented by formula (X), or the group represented by formula (X3).

15. A curable composition comprising: The photochromic compound of claim 1; and Select at least one from the group consisting of free radical polymerizable monomers, cationic polymerizable monomers, compounds having polymerizable reactive groups, and (thio)carbamate (urea) polymers.

16. A cured product, which is a cured product of the curable composition of claim 15.

17. An optical article comprising the cured material of claim 16.

18. A lens comprising the photochromic compound of claim 1.

19. A pair of eyeglasses comprising the lens of claim 18.

Images